DE2260194A1 - PHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

PATENT LAWYERS DR.-ING. WOLFF, H. BARTELS, DR. BRANDES, DR.-ING. HERO Dipl.-Phys. Wolff

Nov 14, 1972

MÖNCHEN 22 THIERSCHSTRASSE 8. ·? r / O TELEPHONE: (0811) 293297 '

Registration number. 123 744

EASTMAN KODAK COMPANY, 343 State Street, Rochester, New York State, United States of America

Photographic recording material

309825/0828

2250194

■ '■ χ

The invention relates to a photographic recording material with a support and at least one light-sensitive A layer whose photosensitive compound is in contact with an image dye-forming compound.

It is known, for example, from U.S. Patents 2,992,105; 2 909 430 and 3 065 074, in the context of photographic transmission processes so-called. Leuco developer compounds to use, which when reacting with silver halide with its reduction to silver, a chromophore between the developer residue and the one attached to it form directly bound residues.

It is also known, for example, from U.S. patents

2 983 606 and 3 255 001, in the context of color photographic processes To use dye developer compounds in which a developer residue is bound directly to a preformed dye residue is.

Finally, it is also known, e.g. from the USA patents

3 230 082, 3 230 083 and 3 307 947, in the frame of color photographic Method of using dye developer compounds that have hydrolyzable groups *

It is further exemplified in U.S. Patent 3,227,552 known, not in the context of image transmission processes to use diffusing compounds which, upon contact with an oxidized color developing agent, form a Release dye.

From U.S. Patents 1,102028 and 2,206,126 are further Leuco compounds known, which reduce silver halide to silver and thereby to colored compounds with a chromophore be oxidized.

309825/0828

/. 22B0194

However, the known Leuco dye systems have in practice is not of great importance, especially not because the known leuco dyes unsatisfactory developer and have dye properties, upon which, for example in Hunt's book "The Reproduction of Colors", published by Fountain Press London, 1967, p. 291.

With regard to the not yet fully satisfactory properties the known color photographic recording materials, for example the still unsatisfactory dye absorption characteristics of the available dyes, the low Development speeds of the materials and the low image resolution, it was the object of the invention to provide new photographic Recording materials, especially for image transfer processes, with improved properties to be found.

The invention was based on the knowledge that the problem can be solved with a new class of compounds, which are very excellent for the production of color photographic recording materials, especially for the production of recording materials and film units for diffuse ion transfer processes are useful and the manufacture of image transfer materials and image transfer film units of various constructions and thereby enabling improved photographic images Deliver characteristics.

The compounds which can be used according to the invention are by a Rest characterized, which is able to form an azomethine or imine chromophore by chromogenic oxidation. By Compounds generated by chromogenic oxidation can either represent the desired image dyes themselves or else further be implemented, for example when the dyes produced by oxidation consist of indophenols, in which case these indophenols are advantageously reacted with an onium compound to produce an onium indophenoxide dye.

3ö98H / 0628

The invention thus provides a photographic recording material with a support and at least one photosensitive layer, the photosensitive compound of which with an image dye forming compound which is characterized as being an image dye forming compound Compound contains an oxichromogenic compound of one of the following formulas:

(OC) -D or
(OC) -binding link- (coupler remainder ballast group) _m

where mean:

D an aromatic silver halide developing agent;

(OC) a chromogenic oxidation into an imino-

dye residue (or azomethine dye residue) transferable residue;

the link is a residue that is oxidized upon contact with an

Splitting off silver halide developing agent;

the coupler radical is a 5-pyrazolone, a pyrazolotriazole, a

phenolic or an open-chain ketomethylene coupler radical, where it applies that the coupler residue in Coupling position is substituted by the link;

the ballast residue is a photographically inert, organic residue

of such a molecular size and configuration, the iHxek is that represented by the structural formula

Non-diffusing compound when developed with an alkaline developing solution makes and

m »1 or 2.

309825/0828

2280194

The residue represented by (OC) may also be referred to as a residue having a reduced imine bond (or reduced azomethine bond) will.

In the case of the oxichromogenic compounds used according to the invention it concerns compounds which through chromogenic oxidation form a new chromophore.

According to a particularly advantageous embodiment of the invention, the oxichromogenic compounds are oxichromogenic developer compounds used, which correspond to the formula (OG) -D, in which D is an aromatic silver halide developing agent and (OC) a residue that becomes an imino dye residue through chromogenic oxidation (or azomethine dye residue) supplies.

The silver halide developing agent represented by D may be hydrolyzable Have residues. It preferably consists of a disubstituted aromatic radical with at least two Substituenteii, those of hydroxyl radicals or hydrolyzable derivatives, for example thereof, from primary amino radicals or optionally substituted Alkylaminores-th can exist.

The remainder (OC) preferably consists of a remainder of the following structural formula:

- (Coupler residue) -N-Ar-X
where mean:

the coupler radical is a common photographic color-forming agent

Coupler rest that is in coupling position by a Carbon atom is bonded to the nitrogen atom, e.g. a phenolic coupler pyrazolone,

Pyrazolotriazole or open chain coupler / with

rest

300326/0828

2260134

active methylene groups, in particular a residue of a soluble color coupler with solubilizing residues, which make the color coupler diffusible;

Ar is an optionally substituted arylene radical having preferably 6 to 20 carbon atoms, which is optionally can be built up from two or more condensed arylene radicals, but preferably from consists of a phenylene radical which can be substituted in an advantageous manner, for example by hemogen atoms or radicals containing halogen atoms in the ortho or meta position of the ring and

X is an optionally substituted amino radical or, preferably a hydroxyl radical.

Advantageously, in this embodiment form of the invention Oxichromogenic developers are used, which are diffusing and are able to diffuse in image receiving layers, if the Developer residue is not oxidized by reaction with developable silver halide or by a redox compound. In advantageous In this way, image-receiving layers are used which contain an oxidizing agent or are in contact with an oxidizing agent, which enables the chromogenic oxidation of the oxichromogenic compound.

A photographic recording material advantageously has according to the invention at least one light-sensitive Silver halide emulsion layer.

According to a particularly advantageous embodiment of the invention, the recording material consists of a layer substrate with at least a silver halide emulsion layer coated with an oxichromogenic Developer compound of the structure described is in contact, an image receiving layer and an onium salt.

J 0 9 β 2 B / U θ 2 8

22-094 - / -

The chromophore of the oxichromogenic developer compound can by Oxidation by air or by oxidation with an oxidizing agent present in the image-receiving layer or is in contact with them.

According to a further advantageous embodiment of the invention contains the recording material suitable for image transfer processes according to the invention is an immobile or non-diffusing compound with a radical of the formula (OC) -. In this case becomes an oxichromogenic residue with a considerably lower molecular weight set free in relation to the immobile or non-diffusing compound or by reaction of the compound with a silver halide developing agent, for example by a redox reaction. or by coupling reaction with a Color developing agent such as a primary aromatic amine color developing agent diffusing made.

According to a particularly advantageous embodiment of the invention If the recording material contains one or more stabilized oxichromogenic compounds, which are against a premature or too early oxidation are stabilized.

Such stabilized oxichromogenic compounds are those of the formulas given, in which the remainder (OC) has the following

Formula has: -

R ^z

- (Coupler residue) -N-Ar-X

in which the coupler radical, Ar and X have the meaning already given, with the proviso that X is also a radical of the formula: '

-0-R ¹

may be where R is a radical containing a carbonyl group can, for example, a residue of the formula:

3Q9g2b / Q828

2250194

-CR ⁴

4th
wherein R is an organic radical having 1 to 12 carbon atoms, in particular an optionally substituted alkyl or aryl radical, and furthermore

2 1

R is a hydrogen atom or a radical as defined for R is »provided that at least one of the radicals R

2
and R is a radical having a carbonyl group.

Oxichromogenic compounds of the various

4th
given structural formula in which R is a halogenated alkyl radical, in particular a trifluoromethyl radical.

In this embodiment of the invention, the oxichromogenic compound can undergo an oxidation catalyzed by a base.

2 1

gen, where the stabilizing radicals R and / or R by a strong base can be hydrolyzed so that oxidation can take place.

The stabilized oxichromogenic residues can be attached to a non-diffusing coupler or bound to a developer residue.

According to a further particularly advantageous embodiment of the invention the recording materials have at least one oxichromogenic compound and an incorporated silver halide auxiliary developer compound, for example a pyrazolidone developing agent.

According to a further particularly advantageous embodiment of the ER invention the recording materials have at least one oxirhromogeneous Compound and at least one developer compound releasing an inhibitor.

3 09826/0828

226Q114

The residue defined by Ar is preferably the residue of a usual one aromatic color developing agent, for example an aminophenol or a phenylenediamine, the aromatic Residues can be substituted in a conventionally known manner.

Particularly advantageous compounds are present when Ar is the nucleus of an aminophenol developer compound. The aromatic one The remainder can be substituted in the manner described in the US patent application with Serial Mo. 169 706

is known.

If compounds of the formula (OC) -D are used, the oxichromogenic radical preferably has an isolating bond, via which the remainder is connected to the developer residue (D). Insulating bonds are to be understood as such bonds which are sometimes referred to as so-called achromophoric groups or bonds and, for example, from the USA patent 3 255 001 are known. Such isolating bonds or groups do not provide any color-producing groups in the through chromogenic oxidation generated dye molecule. They serve rather, the formation of a conjugation system or resonance system, that from the azomethine group of the oxichromic residue to the developer residue, i.e. e.g. B. a hydroquinone residue to prevent or interrupt. .This makes any influence of the developer residue on the color characteristics of the azo- 'methine group is effectively eliminated. Such insulating bonds or groups which preferably form part of the oxichromogenic radical can thus be made up of any radical or any Group that break the resonance system, for example a group of that known from US Pat. No. 3,255,001 Type.

■ '■ m

Here, an "azomethine residue" is a residue of the following formula to understand:

(r: C-N-)

which is often referred to in the chemical literature as the "imine residue" will.

The dye-forming or oxichromogenic used according to the invention Compounds thus have a residue which upon oxidation forms an imine or azomethine residue, which is used as the chromophore of Imine or azomethine dyes can be designated.

The dye-producing or oxichromogenic used according to the invention Compounds thus have a "reduced azomethine residue" or a "reduced imine residue", as follows Structural formula corresponds to:

R ²
(^ CN-)

where R has the meaning given.

Some of the azomethine compounds that can be produced according to the invention can also referred to as indophenols, which are compounds of the following structural formula;

(Coupler residue) -N-Ar-OH

in which the coupler radical is a color coupler radical, in particular a pyrazolone, pyrazolotriazole, open-chain ketomethyleη or phenolic color coupler residue bound to the nitrogen atom in its coupling position. Ar has the meaning already given.

) Ü <JH 2 b * / 0 ΰ 2 8

The term "non-diffusing" refers to compounds non-diffusing in the usual sense in the field of color photography are, i.e. not through organic colloid layers, for example gelatin layers, from which color photographic Recording materials are built up, migrate or diffuse. The term "immobile" has the same meaning.

In contrast, "diffusing" is used in color photographic In the usual sense, compounds are understood which have the property of being effective through colloid layers of a recording material in the presence of "non-diffusing" compounds to wander or diffuse. The term "mobile" has the same meaning.

Typical dye (producing or oxichromogenic compounds that for the production of recording materials according to the invention are for example:

- 11 -

link

formula

Melting point

OH

O CH ₂ CNI!

- NHC

NH

OH

CH ₃ COOH

on ^C 5 ^H 11

225-227 ^u C

011

OH

(CH ₂ ) CONH

NHCO

Cl J Cl

OH 219-222 ^U C

* = N-anyl

309825/0828

C ₆ H ₅ M

OH

17Ö «176 ⁰ C

HO

J ₄ CONH

M-CONH

OCH

130 »ISO ⁰ C

OCHCONH
NH

2210194

JtH

OH

(CH ₂ ) ₄ CONH

HCOCHCOCfCH *) _t NH

90 ⁰ C

OH

VII

(CH) .C0NH 2 *

OH Cl

HCOCHCOC (CH,

I *

NH

92-96 ⁰ C

OH OH

VIII

-T vV ^

115 ⁰ C

OH NHC0CHC0C (CH _t )

NH

3'3

309625/0828

-f-

The stabilized compounds that are used according to the invention as oxichromogenic developer compounds can be used include for example:

OH

(CH ₂ ) ₄ -CONH

NHCO

4 V ^C 5 ^H 11 *

171-173 ⁰ C

NCOCF.

Cl γ Cl OH

OH

+ = Anyl

(CH ₂ ) ₄ CONH

OH

3Ü9B2b / ÜB28

OH

N N

CH ₂ CONH ^ \ CONH

-COCF.

OH

Cl j Cl OH

OH

(CH ₂ ) - C-NH

H . S.

er ^ r ei

-C-ΓΗ,

OH

CH

(CH ₂ ) ₅ CONH

8O ⁰ C

N N

Il

C-NH

OH NH

"'T Cl

OCOCH

2 Z ₁ ο y I §

OH

110-117 ^u C

(CH ₂ ) ₄ -C -NH

OH

OH

N.

H ^V11 3

NH

112-114 ⁰ C

Cl

0C ~ CH

Il

XVI

OH

(CH ₂ ) ₄ CONH

OH

N N

'N

COCF

H,

Cl "T Cl

OC-CH- 3

XVII

OH

(CH ₂ ) ₄ CONH OCH.

, COCHCONH I
N-COCF

9O-95 ° C (dec.)

OH

OH

XVIII

(CH -) .- C-NH-

• * Il

NH-C-CH-C- C- (CH ₁ ) -

HIM JJ

0 NH 0

78-8O ⁰ C

30082Ε / 002Θ

OH

XIX

(CH ₂ ) ₄ CONH

NHCOCHCOC (CH ₃ )
N-COCF,

215-216 ^U C

Cl T Cl
OH

OH

(CH ₂ ) ₄ CONH

SO ₂ NH

OH NHCOCHCOC (CH ₃ ) N-COCF,

131-136 ° C

Cl j Cl

OH

OCH.

XXI

NHCOCHCO NH

OH

12O-130 ° C

NHCO (CH ₂ )

Cl

OCOCH

OH

3D 9 Ö 2 & / f) 8 2 β

l / r

260194

Cl

XXII (CH ₃ ) ₃ CCOCHCONH

NH

OH

HCO (CH ₂ ) ₄

he y ci

OCO (CH ₂ ) ₆ CH ₃

OH

90 ⁰ C

XXIII

Cl

(CH_) _ CC0CHC0NH NH

Cl

OH

HCO (CH ₂ )

Cl

0C0C, H _c 6 5

OH

OC ₂ H ₅

0 0 (CH_), C-C-CH-C-NH

NH

Cl

OH

1IC (CH,) O

Cl

OH

OC-CH, t >> -3

120 ⁰ C

226019A

The salts of the oxichromogenic compounds are distinguished by a further improved stability. Usually they are but not quite as stable as the specified acylated compounds. A typical salt of an oxichromogenic compound has the following formula:

XXV.

0 .CH ₂ C-NH

177-18 (TC

.CH ₃ COOH

The compounds used according to the invention can be Manufacture using customary chemical methods: compounds of

Formula:

D - (Kupp) - N - Ar - X in which:

D is the residue of an aromatic silver halide developing agent;

Kupp the remainder of a pyrazolone, pyrazolotriazole, open chain Ketomethylene or phenolic coupler;

an arylene radical with 6 to 20 carbon atoms;

309025/0 8 ^ 8

Hydroxy, amino or AiKylaminrest and

. a

-20a -

- rf-

R is a hydrogen atom or a carbonyl group Rest,

can be produced, for example, by

1) a silver halide developing agent, the aromatic radical D of which is polysubstituted by hydroxy, amino and / or alkylamino radicals and whose hydroxy, amino and / or alkylamino radicals are masked, condensed with a color coupler, that he

2) the condensation product to form an azomethine group in the coupling position of the coupler condensation product reacts with a primary aromatic amine and that man

3) the reaction product is reduced with cleavage of the masking residues.

man
Advantageously, a silver halide developer compound can be used in which the hydroxy, amino and / or alkylamino radicals are masked by carbobenzoxy radicals.

One can, for example, also proceed in such a way that the condensation

ation product of silver halide developing agent and color coupler to form a reduced azomethine group in the coupling position of the coupler condensation product with a primary aromatic Amiη converts and the reaction product obtained before splitting off the masking residues with at least a three-fold molar excess of one, if necessary polyhalogenated »acylating agent acylated. In advantageous Way you can remove the masking residues by catalytic hydrogenation split off and trifluoroacetic acid as acylating agent use «Acylation can, for example, result in the formation of N-acyl residues in a polar solvent under acidic or weakly basic conditions

- 20b -

309Ö2E / 0829

50194

Yellow image dye-forming compounds according to the invention with a ketomethylene coupler radical can be prepared, for example, by reacting a ct-halogenated open-chain ketomethylene dye coupler with an aminophenol of the formula NH ₂ -Ar-OH by reacting the compound obtained with a reduced azomethine group with an acid chloride Stabilization of the reduced azomethine group is 0-acylated and that the compound obtained is optionally condensed with a masked silver halide developer compound and then the masking residues of the silver halide developer residue are split off. Advantageously can be the O-acylation with the acid chloride in a basic, non-aqueous polar solvent to carry and operate at temperatures from -20 to +20 ⁰ C.

Purple image dye forming compounds of the foregoing Formulas in which the color coupler residue is from a 5-pyrazolone or pyrazolotriazole color coupler radical can be prepared accordingly, for example, by

a corresponding halogenated 5-pyrazolone or pyrazolotriazole color coupler, optionally with a masked silver halide developer residue with an aminophenol, in particular p-aminophenol, converts to form an azomethine compound that one

the azomethine compound to form an oxichromogenic developer compound reduced that one

the developer compound is acetylated and that optionally

cleaves off the masking residues of the silver halide developer residue.

The stabilized oxichromogens which can be used according to the invention Compounds hydrolyze in all media, i.e. at pH

3Ö8Ö2 & / Ü828 ■ - 20c -

IK

Values from 9 to 14, preferential prices at pi'-l '.' Crtcn of iibat 12 and produce an azomethine dye in the presence of an oxidizing agent or air. Admits the Azomethinfnrhstoff of an indophenol dye, it is preferably during the Hntvickl unp.sprozesscs the photographic On zc'i chnunpsnnterials with a Oniumverhindung pebrncht in contact, so that a "" Oniumindophenoxid can arise. Advantageously, the stabilizing residues are of low molecular weight, so that the diffusion rate of the heart disease is not adversely affected in disruption systems.

For the production of photographic recording materials according to According to the invention, those dye-forming substances are also suitable Compounds that have oxichromogenic residues, which are called oxide

- 21 -

BAO ORIGINAL

! ■) H V b / 0 H 2 H

tion to form indoaniline dyes.

Advantageously, those which can be used according to the invention can be used Dye-forming compounds are stabilized by a hydrolyzable residue on the reduced azomethine nitrogen atom sits.

A typical compound of this type of the general formula:

(OC) -D
is the following compound XXVI:

XXVI

OH

OH

(CH ₂ ) ₄ C-HN

Photographic recording materials to which oxichromogenic eLn N-dialkylindoaniline 'forms the basis of both compounds generally does not result in any further benefit from the presence of onium salts in the image receiving layer, i.e. in this case the presence of onium salts does not cause any control or change in light absorption and image density, as in the case of Indophenol dyes.

The oxichromogenic compounds used according to the invention, in particular the developer compounds of the formula:

30 9 8 20/082 8-

(OC) -D

are excellent for performing image transfer processes. Those which can be used according to the invention Oxichromogenic developers of the type described are quite general diffusible in alkaline media.

The use of those described has proven to be particularly advantageous Developer compounds for the production of color photographic Recording materials for the diffusion transfer process proven, wherein the oxichromogenic developer compounds advantageously in silver halide emulsion layers or be accommodated in adjacent layers. Recording materials of this type can after image-wise exposure by treatment with an alkaline developing liquid which are the silver halide emulsion layer or silver halide emulsion layers and, if necessary, this penetrates adjacent layers with development of the exposed silver halide. In the districts where the silver halide emulsion layer or layers have been developed, the oxichromogenic developer compounds are not made diffusible, i.e. relative to the oxichromogenic developer compounds still present, which diffuse imagewise in image-receiving layers assets in which they can be fixed by pickling. In the oxidation of the oxichromogenic residue, which is preferably carried out in takes place near or in an image receiving layer, a new one is created Chromophore generated with the formation of an azomethine dye.

If the (OC) residue forms an indophenol, it has proven to be advantageous proved to produce the recording material using an onium salt, which is preferably in such concentrations is used that the transferred indophenol is converted into an onium indophenoxide. Advantageously, the. Onium salts before the development process from the oxichromogenic compounds kept away.

3 09Ö2E / 0828

-yf- ΙΎ

Is the onium compound immobile or has a ballast group? and when present in the image-receiving layer, it is expediently used in concentrations of from about 25 to about 1000 mg per 0.0929m layer support surface, especially in concentrations from about 50 to about 500 mg used per 0.0929 m of substrate area, the most favorable concentration in individual cases, of course, depending on the ratio of the onium atoms to the molecule, not the one used Connection depends. Used the onium salt in the form of a solution used, for example in the developing solution, it has been found to be expedient to use concentrations of about 0.01 to about 5 Cew-i onium salt to be used based on the weight of the solution.

The developer residue D is generally for changes in the Diffusibility of the oxichromogenic developer compounds is responsible. By oxidation by reaction with exposed silver halide or an oxidized auxiliary developing agent it preferentially oxidizes to a relatively immobile form.

Such compounds of the formula have proven to be particularly advantageous (OC) -D, in which D is a polyhydroxy-substituted aromatic silver halide developer residue, preferably a hydroquinone developer residue is. The recording materials according to the invention can optionally also be composed of black and white or monochrome Recording materials exist, for example only a silver halide emulsion layer and an oxichromogenic developer compound that lead to the desired color effect.

Of particular importance are subtractive chromatic recording materials, for example three color materials with a blue-sensitive emulsion layer which contains an oxichromogenic developer compound which is capable of forming a yellow chronophore by chromogenic oxidation or which has a layer with it. a solehe ^first · "oxichroriogenen unwinding cVlerverbindung in contact, further

3Q9 8.2 & / 0828

If

with a green-sensitive emulsion layer that is an oxichromogenic Contains developer compound which is able to form a purple chromophore by chromogenic oxidation or which with a such a developing agent-containing layer is in contact and with a red-sensitive emulsion layer which is a contains oxichromogenic developer compound, which is capable of forming a blue-green chromophore by chromogenic oxidation or which with one containing such an oxichromogenic developer compound Layer is in contact.

The oxichromogenic developer compounds used according to the invention absorb no or at most insignificant amounts of light in the visible range of the spectrum, which is why they reduce the exposure of the Emulsion layers in which they are contained or of the Developer compounds do not affect the emulsion layers arranged relative to the direction of exposure by the layers. As a result, the oxichromogenic developer compounds used in the present invention can be used in silver halide emulsion layers themselves or housed in layers over the emulsion layers and the like will. Because of these properties of the developer compounds, it is possible to produce recording materials for the image transfer process of very different structure, i.e. differentiate the developer compounds used according to the invention are extremely advantageous due to their properties described from the known dye developer compounds, the contain a pre-formed dye residue. When such dye developing agents are used, the arrangement is well known of the compounds under the respective emulsion layer relative to the Reloading direction required in order to avoid undesired light absorption and consequently a loss of sensitivity.

oxichromogenic compounds never used according to the invention are suitable is particularly suitable for the production of recording materials of the most varied Type for the diffusion transfer process

3Ö9S2S / 0828

originally diffusible developer compounds or originally non-diffusing compounds are used together with silver halide emulsions, e.g. materials from
U.S. Patents 2,543,181; 2,983,606; 3,227,550;
3,227,552; 3,415,644-3,415,646; 3 635 707, Canadian
674 082 and Belgian patents 757 959 and 757 960.

On the other hand, however, the photographic recording materials according to the invention can also contain non-diffusing compounds the formula:

(OC) -binding link- (coupler remainder ballast group) _m

- 25 -

30982B / 0828

3fr

have, where the remainder (OC), the bark link, the coupler residue, the ballast group and m have the meaning already given and which set free an oxichromogenic compound by redox or coupling reaction with an oxidized developer compound. In the case of these compounds, the oxichromogenic radical is bound to a coupler radical having a ballast group, through a link which cleaves off when the coupler radical having a ballast group comes into contact with an oxidized silver halide developer compound, with a diffusing, an image dye-producing or forming substance being a A considerably lower molecular weight is produced in relation to the starting substance, ie a compound whose molecular weight is reduced by at least 10%, preferably by at least Z0%, compared to the starting substance.

According to a particularly advantageous embodiment of the invention, the aichromogenic radicals can be linked to a sulfonyl radical Hydroquinone residue be bound with a ballast group. Referred See, for example, US Pat. No. 3,698,897.

According to a further advantageous embodiment of the invention, the oxichromogenic radicals can be one of a sulfonamido radical existing link may be bound to a phenolic radical having a ballast group. Reference is made to this, for example to U.S. Patent Application Serial No. 176 752.

The oxichromogenic residues can, however, also via other links be bound to non-diffusing couplers as described in more detail below. The non-diffusing Couplers can have, for example, cleavable oxichromogenic indophenol residues. Such ballast groups are of particular importance containing compounds which are non-diffusing or practically non-diffusing in alkaline media and which are used in Contact with an oxidized

- 26 -

309025/0028

Winder compound a diffusing oxichromogenic residue in Set freedom. Typical suitable compounds of this type are compounds different from phenolic couplers and acylacetanilide couplers and can correspond, for example, to the following formulas:

1) phenolic couplers (including naphtholic couplers) of the following compounds:

OH

• CNH (CH _{2) 4} 0

-t

O
NHCCH ₂ O

OC (CH ₇₎ -CR ¹ O

^J 5 ^H 11

-t

0 0
NHC (CH ₂ )

CO ₂ H

309825 / Q828

and

/ Λ

where X can be a residue of the following formulas:

0

-OC (CH ₂ J ₂ CR ₁

or -NHSO

NHC (CH ₂ ) ₂ CR

2) Acetanilide

Cl

O 0 \

(CH-J-CCCHCNH-H ' ^XN

and

O-

OCH,

ο ο V-,

ti ι « // Λ CCHCNH-V

where Y is a residue of the following formulas:

Il

O -OC (CH ₂ J ₂ CR ¹

/ ν

or

"° ~ \ / ~ ^C0 2 ^H

/ θ O

NHC (CH ₂ J ₂ CR

,1

with the proviso that R and R are, for example, a radical of the following Formula can be:

309825/0828

- yr- 33

NHC

Cl T Cl OH

it also applies that R is, for example, also a residue of can be the following formulas:

-HN-

ο ο

MHCCHCC (CH,).

NH

Cl

CL

OH

or

909Ö25 / 0S28

Cl

Other typical non-diffusing couplers to which the oxichromogenic Residues that may be bound are, for example, those described in U.S. Patents 3,227,551, 3,227,550, and 3,227,554 Coupler.

Leave the non-diffusing couplers with oxichromogenic residues from the corresponding Bailastgruppen having couplers produce.

Advantageous Non-Diffusing Couplers That Can Be Used In Manufacture Photographic recording materials suitable according to the invention are, for example, those of the formula:

-, 10 -

309825/0828

226019η

3Γ

(OC) -link- (coupler remainder ballast group)

in which (OC) has the meaning already given and in which also mean:

1) The link, a residue that splits off when the coupler is in contact with an oxidized silver halide developing agent comes, preferably an azo, mercury, oxy, alkylidene, thio, Dithio-, azoxy-, sulfonamido, aminoalkyl- (see for example U.S. Patent 3,419,390), sulfonyl-, sulfonyloxy- (see for example US Pat. No. 3,415,652), acyloxy (see, for example, US Pat. No. 3,311,476) or an imino radical, e.g., of the type known from U.S. Patent 3,458,315;

2) the coupler radical is a conventional coupler radical, for example a 5-pyrazolone, a pyrazolotriazole, a phenolic coupler or an open-chain ketomethylene coupler radical, where the coupler radical is substituted in the coupling position by the link;

3) the ballast group is a photographically inert organic ballast group of such a molecular size and configuration that the coupler is non-diffusing in an alkaline developing liquid during the development process and

4) η »1 or if the link consists of an alkylidene radical 1 or 2. ■

In general, the diffusing radicals of the compounds have acidic solubilizing radicals, those of such solubilizing radicals Residues can exist which, if they sit on the dye-generating residue, the resulting dyes in alkaline Make developing fluids diffusible. Typical residues of this type are carboxyl and sulfonic acid residues as well as ionizable ones Sulfonamide radicals and radicals substituted by hydroxy radicals,

which give the dyes negative charges.

The nature of the ballast group in the diffusing dye-generating agent Compounds is not critical as long as it makes the coupler compounds non-diffusible. Typical Ballast groups are long-chain alkyl radicals that can be bound directly or indirectly to the coupler molecules, as well as aromatic ones Remnants of the benzene and naphthalene series, which are bound directly or indirectly to the coupler molecules by splittable groups can. In general, suitable ballast groups have at least eight carbon atoms.

The "coupling position" of the coupler compounds which can be used is known. 5-pyrazolone couplers are known to couple at the 4-position located carbon atom. The phenolic couplers, including the known α-naphthol couplers, also couple on the carbon atom in the 4 position. The open chain ketomethylene couplers couple on the carbon atom that forms the methylene radical, i. on the one marked with a "+" in the following structural formula Carbon atom:

0
-C-CH ₂ -

The coupling position of pyrazolotriazole couplers is, for example from U.S. Patents 3,061,432 and Belgian Patent 724 427 known.

The coupler remainder in the formulas:

(OC) -D and

(OC) -binding link- (coupler remainder ballast group) _m

can also consist, for example, of a coupler residue of the type known from US Pat. No. 3,620,747.

3Ü982 & / 0828

Become a coupler of the formula:

(OC) -link- (coupler remainder ballast group)

reacted with oxidized color developing agents, it will be Link split off and a diffusing connection in freedom set consisting of a dye image-forming compound exists, which is able to diffuse imagewise into an image receiving layer. The diffusibility of this compound can thereby caused by solubilizing residues «the ballast groups exhibiting part of the coupler remains immobile. In the event of such recording materials will be the color of the image dye determined by the chromophore generated in the development process.

When using recording materials according to the invention with the described color couplers is the creation of a diffusing one an image dye-forming compound is a function of Reduction of developable silver halide images, with a direct or an inverse development of the silver halide emulsions with a developing compound consisting of a primary aromatic amine can be carried out. Passes the silver halide emulsion layer or the silver halide emulsion layers of the recording material according to the invention consist of one or more direct positive silver halide emulsion layers, for example Internal image or internal grain emulsion layers or solarizing Emulsion layers that can be developed in the unexposed areas positive images can be found in the image receiving layer or an image receiving part of a photographic film unit. The non-diffusing color couplers can be in the silver halide emulsion layer or the silver halide emulsion layers be housed yourself. After exposure of the recording material, which can optionally form a film unit with an image receiving element, the development takes place by means of an alkaline developing liquid, which the Layers of Aufziehnxingsmaterials penetrates, namely under

3098 2S / 0828

Initiate the development of the exposed layer or layers. The developer compound is oxidized imagewise, corresponding to the unexposed areas of the direct-positive silver halide emulsion layer or layers. The oxidized developing agent then reacts with the layer or layers the non-diffusing couplers which diffusible in the silver halide emulsion layers or the can be accommodated, imagewise distributions to form dye images providing compounds, as a function of the imagewise exposure of the silver halide emulsion layer or. At least some of the diffusing image dye-generating compounds present in an imagewise distribution then diffuse into the image-receiving layer, whereupon dye images are generated by oxidation, if appropriate upon contact with an onium compound.

Advantageously, the recording materials according to the invention can have a pH-reducing layer by means of which the pH of the recording material or the film unit is reduced after contact with the alkaline developing liquid while stabilizing the recording material. For further details with regard to non-diffusing color couplers and the chemistry of the processes occurring in the case of recording materials using color couplers, reference is made, for example, to US Patents 3,227,550 and 3,227,552.

According to a further advantageous embodiment of the invention disclose the described non-diffusing color couplers to produce diffusing image dye-forming compounds together with couplers that set free development inhibitors, as described, for example, in U.S. Patent 3,227,551 are used.

In this embodiment of the invention, the photographic Recording material of the invention at least two color-forming Units facing different areas of the visible Spectrum are sensitive and which are characterized by a separating layer

309826/0828

260194

a hydrophilic colloid with a reaction component that is insoluble in water, which is able to form a water-insoluble salt with a mercaptan, are separated. Can advantageously these color-forming units each be constructed from;

1) an escape CLCE Ib arene Emuls ions see eh tjaos a-hydrophilic colloid and a la? Ass @ r insoluble metal salt of _D that to be subjected to suit light without the exposure ₀ @at by means of a p-Aminophenolfarbentwicklerverbindimg to a detectable or significant density ? iiclc @ lt, where the metal salt is in contact with a non- _{diffusing color coupler la, (} which is able to react with oxidized color developing agent to form a diffusing compound which produces or supplies an image dye

Is capable of reacting a photosensitive emulsion layer, the silver halide having a non-diffusing a developing country bitor in freedom releasing coupler is in contact _v tirelcher with oxidized color developing agent to Infreiheitsetzen a diffusing mercaptan Entwicklimgsinhibitors 2) which biidweise to diffuse into the adjacent developable emulsion layer to inhibit the development process able to

As a developer compound are preferably primary aromatic amine developing compounds' are used which are placed in the alkaline processing liquid for use _0th The developable emulsion layer preferably consists of an emulsion of a hydrophilic colloid "silver thiocyanate and physical development nuclei", with the proviso that the emulsion layer can be developed to considerable or considerable density without exposure to light Metal salt can be produced, which can thereby be made spontaneously developable. Notice that physical development nuclei are incorporated into the emulsion - as shown, for example, in column β _s lines 63 to? 75, and column T _0, lines 1 to 10 of the United States patent

3,227,551. Another method which can be used to render the water-insoluble salts spontaneously developable consists in _pre-fogging the emulsion with light or by means of a chemical reducing agent, for example an alkali metal borohydride, according to conventionally known photographic fogging methods.

According to a further embodiment of the invention, the described non-diffusing couplers in combination with physical development nuclei are accommodated in a seed layer, whereby each light-sensitive silver halide emulsion layer to form a diffusing image dye-forming compound is in contact with such a seed layer. The recording material or the film unit formed from the recording material further contains a silver halide solvent which is preferably arranged in a splittable container with the alkaline developing liquid. Furthermore, each contains light-sensitive silver halide emulsion layer an immobilizing coupler such as a coupler having a ballast group, which is able to react with an oxidized color developing agent to form an immobile reaction product. Each of the photosensitive silver halide emulsion layers and its associated seed layer are different from the other silver halide emulsion layers and their associated seed layers through separating layers permeable to alkaline solutions, which perform the task have to withhold silver complexes, separated.

After exposure of the recording materials or those resulting therefrom The film units formed penetrates the one used for development alkaline developing liquid covers the various layers, initiating the development of the latent images of the photosensitive Silver halide emulsion layers. The one to develop the color developing agent used in the film unit develops each of the exposed silver halide emulsion layers, whereby the color developing agent is imagewise

309828/0828

2160194

is oxidized. The oxidized developing agent then reacts with the immobilizing coupler in each of the silver halide emulsion layers producing immobile reaction products. The remaining silver halide in each of the silver halide emulsion layers, corresponding to the unexposed and consequently undeveloped areas forms a soluble silver ion complex with the silver halide solvent contained in the developing liquid can be present or can be activated by these, whereupon the silver complexes in the assigned or neighboring germ layers migrate. In these seed layers the transferred silver complexes are reduced or physically developed, thereby oxidizing the developing agent. The oxidized developing agent can then be mixed with that in each seed layer existing non-diffusing couplers react, namely under image-wise splitting off of oxichromogenic compounds, for example a diffusing oxichromogenic that produces a blue-green dye Compound, an oxichromogenic compound providing a purple dye, and a yellow dye providing oxichromogenic compound as a function of the imagewise exposure of each of the silver halide emulsion layers. At least part of the diffusible ones present in an image-wise distribution oxichromogenic compounds then diffuse into the image receiving layer, in which positive dye images then arise through oxidation, possibly also through contact with an onium compound.

The recording materials advantageously have a the pH-reducing layer, whereby the pH-value of the Recording material or the film unit after being brought into contact with the alkaline developing liquid with stabilization of the recording material or the film unit is reduced.

The physical development nuclei can be known from the usual physical development nuclei exist, for example those from metals present in colloidal form, for example

30 9 825/0828

se of colloidal silver, gold, platinum, palladium or of metal sulfides present in colloidal form, for example colloidal silver sulfide or zinc sulfide. Compounds that contain physical development nuclei can also be used provide, for example, reducing agents and compounds containing a labile sulfur atom. The seed layers can also form two sub-layers, the two sub-layers being accommodated on different sides of the silver halide emulsion layer are. As the silver halide solvent, conventionally known silver halide solvents can be used, for example an alkali metal or ammonium thiosulphate or a corresponding thiocyanate, for example sodium thiosulphate »ammonium thiosulphate, Ammonium thiocyanate or potassium thiocyanate. These silver halide solvents may optionally be used in a particular one Shift.

Advantageously, there are separating layers between the seed layers and the light-sensitive silver halide emulsion layers arranged to avoid mixing of the two layers during the production of the recording material. These Separating layers can optionally also contain nuclei, and furthermore a non-diffusing coupler, the one with oxidized color developing agent able to react to form an immobile reaction product in order to increase the effectiveness of the recording material or the film unit. Regarding the structure such photographic recording materials and film units are also referred to, for example, to the British Patent specification 904 364, in particular page 19, lines 1 to 41 referenced. When using recording materials with non-diffusing Color couplers can advantageously be used between the various light-sensitive color-forming units Intermediate layers are arranged, which have the task of intercepting oxidized developer compound or rendering it harmless, thereby avoiding the formation of undesirable dyes in the other color-forming units. Such intermediate layers

309825/0828

-/-fa

can advantageously be composed of a hydrophilic polymer, for example gelatin, and an immobilizing coupler of the type already described, which is capable of reacting with oxidized color developing agent to form an immobile reaction product. Such intermediate layers can
furthermore bind or scavenge other compounds and substances, for example soluble silver ion complexes or mercaptans, whereby it is prevented that such compounds or substances
contaminate other color-forming units.

An intermediate developer scavenger layer may optionally des
further adjacent a light reflective layer to keep excess color developing agent thereon
to prevent the image receiving layer from being contaminated or discolored. Such a layer can be built up, for example
from a non-diffusing coupler, which is able to react with oxidized color developing agent to form an immobile reaction product, and a silver halide emulsion, '
preferably one which can be developed without being exposed.

The dye-providing compounds used according to the invention can be used in concentrations such as those used for the preparation of image dye-forming recording materials are common.

In the case of recording materials according to the invention, in which In the course of the development process indoarylene compounds, for example indophenols, are generated, it has proven to be advantageous proved to bring this into contact with an onium compound with the formation of onium indopliene oxides. The onium compounds can either consist of soluble compounds, so that the indophenols produced with a solution of an onium compound can be brought into contact or else from high molecular weight

309826/082 * - ·

Compounds which are relatively insoluble in water and which can be accommodated in at least one layer of the photographic recording material, for example in the image-receiving layer, in which an onium indophenoxide dye image is then generated from the indophenol.

Typical onium compounds used in the formation of onium indophenoxide dye images are suitable, can consist of quaternary ammonium, phosphonium and sulfonium compounds, such as for example, they are described in more detail in U.S. Patents 3,146,102, 3,212,893, 3,253,915, and 3,266,894.

Particularly advantageous dye images can be obtained by reaction obtained from indophenols with quaternary ammonium compounds.

Quaternary ammonium compounds are known to be organic compounds with a nitrogen atom that carries a positive charge. In general, quaternary ammonium compounds can be used as derivatives are referred to by ammonium compounds in which the four valences, which are normally occupied by hydrogen atoms, are occupied by organic residues. The organic radicals can be attached to the nitrogen atom directly through a simple or through a double carbon-nitrogen formation be bound. "Quaternary ammonium compounds" are also to be understood here, see in which the nitrogen atom is a core atom of a heterocyclic ring, in contrast to such quaternary ammonium compounds, in which the four valences of the nitrogen atom are substituted by separate organic radicals, in which case, for example, compounds of the quaternary tetraalkylammonium type are present.

Quaternary ammonium compounds used according to the invention can be represented, for example, by the following structural formulas:

309826/0828

(D

R.
RN ⁺ -R γ "> / and V * ι R. / \ R. R R

Herein mean:

R is an organic radical;

Y is an anion such as a hydroxy, bromide, chloride or toluenesulfonate anion and

Z are the atoms required to complete a heterocyclic ring.

Compounds which fall under one of the formulas (1), (2) or (3) are, for example, tetraethylammonium bromide, N-ethylpyridinium bromide, Ν, Ν-diethylpiperidinium bromide, ethylene-bis-pyridinium bromide, 1-ethylpyridinium bromide, i-phenethylpyridinium bromide , Tetraalkylammonium salts, cetyltrimethylammonium bromide, polyalkylene oxide-bis-quaternary ammonium salts, e.g. polyethylene oxide-bispyridinium perchlorate, heterocyclic quaternary ammonium salts that form methylene bases, e.g. S-methyl-Z-äthylisoquinolinium-zuisoquinolinium-methyl-1-methyl-sulfynolium-methyl-isoquinolium-methyl-1-methyltholthyl-methyl-isoquinolinium-methyl-1-methyl-tolethyl S- ¹ phenethylbenzimidazolium bromide, 5,6-dichloro-1-ethyl-2-methy1-3- (3-sulfobutyl) benzimidazolium betaine and the pyridinium salts.

Other suitable onium compounds used in the invention are tertiary sulfonium compounds, as well as quaternary Phosphonium compounds, which can be illustrated, for example, by the following structural formulas:

30 382S / 0829

⁺ X "

(R) ₃ S ⁺ X "and

where mean:

R is an organic radical, for example an alkyl, aralkyl or aryl radical and

X is an anion, for example a hydroxy, bromide, chloride or Toluenesulfonate anion.

Examples of suitable tertiary sulfonium and quaternaries Phosphonium compounds are lauryl dimethyl sulfonium p-toluene sulfonate, Nonyldimethylsulphonium-p-toluenesulphonate and Octyldimethylsul £ onium-p-toluenesulphonate, also butyldimethylsulfonium bromide, triethylsulfonium bromide, tetraethylphosphonium bromide, prostitute thylsulfonium p-toluene sulfonate, dodecyldimethylsulfonium ptoluene sulfonate, Decyldimethylsulfonium p-toluenesulfonate and Ethylene-bis-oxymethyltriethylphosphonium bromide.

The onium compounds can be in the form of the hydroxide or in the salt form be used. If the onium compounds are used in salt form, the anion can be derived from any acid. It should be noted, however, that if the anion consists of an iodide anion exists, the iodide anion may have an adverse effect on the emulsion, so take precautionary measures Should be taken, provided the onium salt is contacted with the emulsion, before the development of the emulsion layer is finished. Particularly advantageous results are obtained when bromides are used as onium compounds.

Particularly suitable heterocyclic quaternary ammonium compounds, which form methylene bases in alkaline solutions

309826/0828

diffusing are those of the following general formula:

R®-NC = CH-CH) _n = C-CH ₇ R ¹

where mean:

D the atoms required to complete a heterocyclic nucleus of a quaternary ammonium compound with one or more reactive methyl radicals of the formula -Q ^ R ¹ in one or more of the core positions, it being understood that the other core positions may optionally be substituted, for example those to complete a quaternary Salt of the pyridine, quinoline, benzoquinoline, benzoxazole, benzoselenazole, thiazole; Benzothiazole, naphthothiazole, benzoimidazole or isoquinoline series;

η = 0 or 1;

R is an alkyl, aryl or aralkyl radical of the benzene series or a substituted alkyl, aryl or aralkyl radical of the benzene series, with the proviso that the alkyl radicals are preferably are short chain alkyl radicals having 1 to 4 carbon atoms;

R 'is a hydrogen atom or one of the radicals represented by R and _

X is an OH anion or any acid anion, for example a Br-, CH ₃ SO ₄ - or

Anion. 3Q982E / 0Ö28

- to

The quaternary ammonium compounds can be used alone or in a mixture with one another or in combination with other onium compounds, i.e. any combination of compounds of the formulas (1), (2), (3), (4) and (5) can generally be used, and either in the developing liquid, the recording material or in both.

Typical onium salts that can be used according to the invention and which form diffusing methylene bases are:

i-Benzyl-2-picolinium bromide of I'oimol:

Rr

1-f3-bromopropyl) -2-picolinium-p-toluenesulfonate; i-phenethyl-2-picolinium bromide;

1 -Y-phenylpropyl-2-picoliniumbronii d;

2,4-dimethyl-i-pheniithylpyiidinium broinide; 2,6-Dimethyl-1-phenäthylpyi idiniuinbioinid; 5-ethyl-2-methyl-1-phenethylpyridiniunibromide; 2-ethyl-1-phenethylpyridinium1) tomid;

1- ^ ~ 3- (N-Pyridinium1) romid) propyl_7-2-pi colinium-p-toluenesulfonate the formula ο:; »! -!

^C 3 ^H 6

pTs

Anhydro-1- (4-sul £ obutyl) -2-picolinium hydroxide of the formula:

~ ^CH

OFI

α-Picoline-ß-naphthoylmethyl bromide of the formula

Br

i-ß-Phenylcarbamoyloxyäthyl-Z-picolinium bromide of the formula

. Br

C ₂ H ₄ OCONHC ₆ H ₅

1-methyl-Z-picolinium-p-toluenesulfonate; i-phenethyl-2,4,6-trimethylpyridinium bromide; t-Phenäthy1-4-n-propylpyridinium bromide; 4-Y-hydroxypropyl-1-phenethylpyridinium bromide and i-n-heptyl-2-picolinium bromide.

: JÖ 9 Ö 2 S / 0 8 2 8

According to a particularly advantageous embodiment of the invention the transferred dye images become in an image receiving layer pickled with a polymer with onium residues. Typical suitable Mordants for mordanting the transferred image dyes are, for example, vinyl pyridinium compounds, for example those from U.S. Patent 2,484,430, as well as polymers with quaternary ammonium residues, as for example in the U.S. Patents 3,625,694, 3,639,357, 3,488,706, 3,557,006, and in the Belgian patent specification 729 202 are described in more detail.

Advantageously, a so-called oniuracoacervate dressing agent can also be used as the dressing agent may be used as described in more detail, for example, in U.S. Patent 3,271,147.

A recording material according to the invention can advantageously contain an image-receiving layer which contains a polyvinylpyridine mordant having. Many of those that can be used in the present invention Oxichromogenic compounds can be broken down after chromogenic oxidation excellent pickling with polyvinylpyridines producing excellent stable images.

J09826 / 0828

226P194

The drawings serve to explain the invention in more detail. In detail are shown in:

FIGS. 1 to 4 are diagrams showing the absorption characteristics of oxichromogenic compounds as shown in Examples 1 _? 2.9 and 22 will be described;

FIGS. 5 to 7 show a particularly advantageous film unit forming Recording material according to the invention, including the individual Layers for the sake of clarity star! are enlarged and where the same reference numerals are used to denote the same features were used.

The film unit 1 shown in Figure 5 has a splittable Container 2, which is arranged transversely to the leading edge of the laminate built up from the individual layers of the recording material and is held in position by binding elements 3. These binding elements can be made from a pressure sensitive tape or Like. That includes the corresponding edge of the laminate. The other edges of the photosensitive laminate are sealed, either directly or over / remote to to prevent developing liquid or solution from getting during or after carrying out the development process after breaking the container 1 from the recording material or the Film unit can leak. The splitting of the by impact pressure-splittable container 2 is carried out by passing the recording material or the film unit 1 through the from the two pressure-exerting members 4 gap formed.

As can be seen from Figure 6, the recording material is made or the film unit 1 from a splittable container, dt · τ one alkaline developing liquid 5 with an opacifier or T opacifying agents' and a light-sensitive laminate, which is made up of an upper transparent dec! layer

309ÖH / 0828

6, coated with a layer 7 consisting of a polymeric acid and a timing layer or delay layer 8 composed of a polymer is coated and a photosensitive one Element consisting of a transparent layer support 9, on which are applied: an image receiving layer 10, which with a Oxidizing agent is in contact, an opaque reflective layer 11, preferably one opaque for actinic radiation Layer 12, which can also be a scavenger layer, and also a red-sensitive silver halide emulsion layer 13, which is in contact with a compound providing a cyan image dye, an intermediate layer 14, a green sensitive one Silver halide emulsion layer 15 in contact with a magenta image dye-forming compound, a Intermediate layer 16, and a blue sensitive silver halide emulsion layer 17, which is in contact with a compound providing a yellow image dye.

The exposure of the recording material or the film unit takes place through the transparent cover sheet 6, which is preferably consists of a material which forms flexible layers which are permeable to actinic radiation.

Figure 7 shows a photographic material of the type shown in Figure 6 after processing. The development process was initiated in that the recording material shown in FIG. 6 was passed through the gap of two pressure-exerting members (see FIG. 5, members 4) as they can be contained in a camera. By splitting the splittable container 2, the contents of the container were distributed in the film unit. In Figure 7, the empty split container is represented by 2 ¹ . The liquid contained in the container 2 with an opacifying agent or an opacifying agent was distributed between the delay or timer layer 8 made up of a polymer and the blue-sensitive silver halide emulsion layer 17. After developing and

309826 / 08-28

2200194 S3

Image transfer, a positive image that can be read on the right side can be viewed through the transparent layer carrier 9.

The structural integrity of those shown in Figures 6 and 7 Film unity can be brought about at least in part by the adhesive characteristics of the individual shoulders of the unit » The adhesion between the timer or delay layer 8 of the transparent cover sheet 6 and the underlying layer 17 is, however, less than the adhesion of the other layers of the laminate in order to distribute the developing liquid 5 between to facilitate these two layers.

Photographic materials constituting a film unit according to the invention can be produced in that the individual parts are assembled in an atmosphere in which a Pressure prevails under atmospheric pressure and in which the transparent Cover sheet is sealed with the photosensitive element along the side edges in order to prevent the entry of air. The exclusion of air between the transparent cover sheet and the light-sensitive Element is desirable to prevent air bubbles from being entrained by the developing liquid, which could lead to discontinuities in the positive image produced. Details of the assembly of the individual sub-elements as well other methods of ensuring uniform distribution the developing liquid between the cover sheet and the photosensitive element are described in Belgian patent 711,897.

One constructed from a recording material according to the invention The film unit may further be on the side opposite to the side from which the developing liquid is in the recording material is distributed, contain a liquid trap, through which excess developing liquid and can be kept away from the actual film unit. Such a liquid trap can also be used as a kind of air outlet serve if there is air. Such liquid traps

309826/0828 "

are described in more detail, for example, in Belgian patent 711,899.

From a photographic recording material according to the invention built-up film units can also be developed, for example, according to methods such as those from the Belgian patent 711 898 are known. In these procedures, two sets of pressure rollers are used to move air between them the transparent cover sheet and the photosensitive element to keep away and a particularly uniform distribution of the developing liquid between the transparent cover sheet and the enable photosensitive element.

The transparent cover sheet can furthermore be grooved or corrugated on the side edges, for example in the one from the Belgian Patent 711 898 known way to distribute the developing liquid in a uniform manner between the transparent cover sheet and the photosensitive element to facilitate. If still available after the development has been carried out If water in the film unit is to be removed from it, this can be done, for example, by using a dry layer, which absorbs water or by creating an access to the atmosphere, so that the water still present can evaporate, which is, for example, permeable to water Realize a transparent cover sheet or by using a water-permeable film support for the photosensitive Element or by allowing the water to evaporate through liquid traps of the film unit.

Those for the production of the recording materials or film units The splittable container 2 used may be of a conventionally known structure, for example such a structure as from U.S. Patents 2,543,181, 2,634,886, 2,653,732; 2 723 051, 3 o56 492, 3 056 491 and 3 152 515 is known. In advantageous Way are such splittable containers from a

3Q9Ö25 / 0828

rectangular bag made of a liquid- and airtight sheet-like material, which forms the two Side walls is folded, whereupon the side edges to create a cavity for the developing liquid 5 with the Opacifiers are sealed together. The longitudinal edge 18 is sealed less than the other side edges, in such a way that it splits when hydraulic pressure is applied, so that the liquid contained in the container 5 pour into the film unit by exerting pressure on the outer walls of the container.

As can be seen from Figures 5 and 6, the container 2 is fixedly connected to the remaining parts of the film unit and extends across the leading edge of the recording material, so that at Exertion of a pressure on the container causes the same to be emptied between the timer or delay layer 8 of the transparent cover sheet 6, which is composed of a polymer, and the one below Layer 17 takes place. In the film unit shown in Figure 6, the weakly sealed longitudinal edge 18 is in the direction of the interface between layers 17 and 18 is directed to facilitate emptying of the container.

When performing a multicolor diffusion transfer process using a film unit 1 of the structure shown the unit is first exposed through the transparent cover sheet 6, as shown in FIG. After exposure, the Film unit 1 developed by being passed through the gap formed by the two pressing members 4, wherein the container 2 is split open by tearing the seal 18. The alkaline contained in the container pours out Developing liquid 5 with an opacifying or opacifying agent between layers 8 and 17 of the film unit 1. The alkaline developing liquid penetrates the Silver halide emulsion layers 17, 15 and 13 below imagewise Development of the silver halide contained in the layers.

30982S / Ö828

Ms function of the imagewise exposure of the individual emulsion layers are diffusing yellow, purple and blue-green Rid dye-providing compounds from the image dye-providing compounds Generates compounds which interfere with the silver halide emulsion layers stay in contact. At least a portion of the one yellow, one purple and one red in imagewise distribution Cyan image dye-providing compounds are then diffused onto the image-receiving layer 10, thereby forming a positive dye image due to chromogenic oxidation in the image-receiving layer is obtained. The positive right-hand legible TiId can then be seen through the transparent layer carrier 0 consider the opaque reflective layer 11 as a background. Since the image receiving layer is not from the negative part of the film unit needs to be stripped off, this can add to the development process subjected laminate to stay in contact.

The colorless oxichromogenic compounds used according to the invention allow exposure through the layers of the recording material and at the same time allow the silver halide to diffuse them in the developed areas make, whereby a disadvantageous color contamination, in particular by the oxichromogenic developer compounds, is avoided.

The oxichromogenic developer compounds can according to the invention be incorporated into an emulsion layer or in a Layer can be arranged between the emulsion layer and the light source used for exposure, without an adverse effect Light absorption by the developer compounds takes place, so that highly sensitive photographic recording materials under Use of negative emulsions and those used according to the invention Oxichromogenic developer compounds can be produced.

30982G / 0828

2260114

The oxidation of the oxichromogenic compounds present in the image receiving layers diffuse, for example, by using a porous support adjacent to the image receiving layer or reach the mordant layer, whereby air can pass through the layer support and bring about the chromogenic oxidation can.

In a particularly advantageous manner, however, they are stabilized Oxichromogenic compounds are used, which means that the oxidation cannot take place before the reaction by using catalysis a base is initiated.

According to an advantageous embodiment of the invention, an oxidizing agent is used next to the mordant or image receiving layer arranged. If the oxidizing agent consists of a mobile or movable compound, it is preferably arranged or housed in a layer under the mordant layer, namely in a delay or timer layer to prevent premature oxidation to avoid. Suitable timer or delay layers will be described in more detail later.

However, if the oxidizing agent consists of an immobile compound, so it can advantageously be the mordant layer or the image-receiving layer are incorporated ·, in which case oxidation occurs during pickling of the image dye-providing compounds.

The most varied of conventionally known oxidizing agents can be used Oxidizing agents of inorganic or organic nature can be used, consisting of monomeric or polymeric, mobile or immobile Compounds may exist, typical, suitable Öxidationsmittol are borates, persulfates, ferricyanides, periodates, perchlorates, Tri pdide, permanganate> Dichromates, manganese dioxide, silver halides Benzoquinones, naphthoquinones, disulfides, nitrogen oxides, heavy

- 5 / T- St

metal oxidizing agents, heavy metal oxidizing agent chelates, N-bromosuccinimides, Nitroso compounds, superperoxides and the like.

If necessary, the oxidizing agent can also be accommodated in a special container which is used to effect contact is split between oxidizing agent and oxichromogenic compound.

The oxichromogenic compounds used according to the invention are suitable furthermore is particularly advantageous for the production of recording materials for image transfer processes those compounds providing the image-receiving layer after the development process and transfer of the image dyes into the image receiving layer from the silver halide emulsion layers is separated. In the case of such recording materials the contact with air causes oxidation after the separation of the image receiving member from the silver halide emulsion layers the oxichromogenic developer with the formation of the image dyes. In this case, the recording materials according to the invention can for example, have a structure such as that disclosed in U.S. Patents 2,543,181, 3,266,894, 3,309,201, 2,661,293 and 2,698,244 is known.

In general, the oxichromogenic developer compounds used in accordance with the invention can be used for the production of photographic recording materials of the type which are intended in particular for the use of dye-image-forming compounds which are initially diffusing in alkaline developing liquids, for example for recording materials of the type for their Manufacture diffusing color couplers can be used, as for example in US Pat. No. 2,666! 293 or for their production, for example, diffusing dyes are used, t / ie> ie b : ii:; pLü lüweLie in the USA-P .itentüchri ft 1 VM 66R are described txljr sii their production, for example, Ai E and erring developers Verb indications will be used by »such as:; io beLsplelsirel-to in dux

H) i) Il i 6 / (I tU » BADORiaN / M. - 5.1 -

2260134

sr

U.S. Patent 2,992,105. The oxichromogenic Developer compounds are ideal for the production of photographic recording materials for image transfer χ method of the type described, as they are colorless and directly in Silver halide emulsion layers can be used, whereby intimate contact with the silver halide emulsion upon penetration the emulsion layers with alkaline developing liquid is ensured, whereby the production of a recording material with six layers instead of nine layers, if the usual dye compounds are present, possible will.

It has been shown that oxichromogenic developer compounds des The type used in the present invention are themselves extremely effective developing agents when incorporated into emulsion layers so that the simultaneous use of auxiliary developer compounds not required to achieve rapid silver halide development and immobilization of the oxichromogenic compounds is. It has been shown that the use of auxiliary black-and-white developer compounds which is generally required when using other originally diffusible compounds, for example when using other dye developers in order to provide a rapid redox reaction and immobilization of the dye To achieve connections, xvie them for example from the USA patents 3,192,044 and 2,983,606 are not required when using the oxichromogenic deficker compounds of the invention is.

It has furthermore been shown that the oxichromogenic developer compounds which can be used according to the invention are in the form of an integrated negative three-color pack unit using the same binder for all layers, i.e. the silver halide emulsion layers and intermediate layers can be applied to a layer support with the formation of transfer images from drawn

good quality without undesired interframe effects occurring. As a result, no measures need to be taken to prevent migration of the dye image-providing compounds the strata in which they are originally contained until after the neighboring strata have developed.

However, it has been shown that auxiliary developer compounds can advantageously be used in drawing materials with oxichromogenic developer compounds intended for transfer processes in order to avoid contamination caused by migration of reaction components, e.g. auxiliary developer compounds or oxichromogenic developer compounds, into other layers. Since the development of Silborhalogenidschirhten with oxichromonenon Enti ^T i cklervcrbindungen proceeds very rapidly, auxiliary developing agents alien to the Aufzeichnungsinateri or film units are housed in the H'eise that they only engage with the silver halide layers in contact, when a falling significant development in the Silver halide layers is done. As a result, any developable silver halide present can be developed before significant diffusion of an oxichromogenic developing agent from an adjacent layer into the layer occurs. The auxiliary developing agent can thereby be arranged in the image-receiving layer, whereby migration into the silver halide layers is retarded. The auxiliary developer compound can furthermore be arranged, for example, in or under a delay or timer layer, before the auxiliary developer compound sets free at a certain speed. On the other hand, the auxiliary developer compounds can also be accommodated in intermediate layers or a slowly diffusing auxiliary developer is accommodated in a splittable container which is intended to hold the aqueous developing liquid.

In a particularly advantageous manner, they can be used as slowly diffusing Auxiliary developer compounds, high molecular weight polycyclic compounds are used, preferably those having at least three Bridged or fused rings, such as 5,6,7,8-tetrahydro-5,8-methano-1,4-naphthalenediol and like slow diffusing auxiliary developer compounds of this type are preferably placed in a splittable container with the alkaline developing liquid. Further Particularly suitable developer compounds of this type or corresponding tautomers are, for example, from the USA patent 3,287,129 known. '

In an advantageous manner, the general auxiliary developer connections use which have slowly hydrolyzing radicals, for example acyl and acyloxy radicals, to the reaction of the To delay auxiliary developer compounds in the silver halide layers. .

Typical suitable auxiliary developer compounds include p-methylaminophenol; 2,4-diaminophenol; p-benzylaminophenol; Hydroquinone; Toluhydroquinone; Phenylhydroquinone; 4-methylphenyl hydroquinone; 1-phenyl-3-pyrazolidone and i-phenyl-A-methyl ^ -hydroxymethylpyrazolidone. Also, for example, a variety of auxiliary or accelerator developer compounds described in U.S. Patent 3,039,869 be used. Such compounds can be present in the developing liquid or at least partially in one or more layers of the recording material for Can be applied.

In color photographic recording materials according to the invention the individual silver halide emulsion layers that contain an image dye-providing compound or the are in contact with layers containing an image dye-providing compound from other silver halide emulsion layers in the negative part by layers of, for example, gelatin

- 55a -

3 ö 9 i ti / ö 8 2 a

tines, calcium alginate or such substances as are described, for example, in US Pat. No. 3,384,483 or Layers of polymeric materials, such as polyvinylamides, such as those for example in U.S. Patent 3,421,892 or by compounds such as those in French Patent 2,028,236 and in U.S. Patents

2 992 104, 3 043 692, 3 044 873, 3 061 428, 3 069 263, 3 069 264,

3,121,011 and 3,427,158 are described separately.

Ί09Β2 5/08

The individual silver halide emulsion layers of a recording material according to the invention, for example those consisting of gelatin silver halide emulsion layers, can advantageously have a layer thickness of about 0.6 to 6 microns. The picture dye-providing compounds can be incorporated in polymeric binders which are permeable to aqueous, alkaline solutions, for example gelatin, in the form of special layers with a layer thickness of about 1 to 7 microns, if they are not contained in the silver halide emulsion layers themselves. The polymeric intermediate layers which are permeable to alkaline solutions, for example based on gelatin, preferably have a layer thickness of 1 to 5 microns. Of course, other layer thicknesses can also be used in addition to the specified layer thicknesses.

For the preparation of the individual layers, including the silver halide emulsion layers The usual known other hydrophilic binders can be used as binders in addition to gelatin verden, both naturally occurring substances, for example Proteins, cellulose derivatives, polysaccharides, for example Dextran, gum arabic and the like, as well as synthetic polymers existing binders, such as water-soluble polyvinyl compounds, e.g. polyvinyl pyrrolidone and acrylamide polymers.

The individual photographic emulsion layers and other layers of a photographic recording material according to the invention can also be used alone or in combination with hydrophilic, for water-permeable colloids have other synthetic polymeric compounds, for example dispersed polyvinyl compounds, for example in latex form and in particular those which contribute to increasing the dimensional stability of the photographic materials. Suitable synthetic polymers that can be used to produce the individual layers are, for example from U.S. Patents 3,142 56 8, 3,193,386, 3,062,674,

2Q982 &. / Q828 · - '

3,220,844, 3,287,289 and 3,411,911 are known.

Water-insoluble polymers have proven to be particularly effective from alkyl acrylates and alkyl methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates, in particular those which have cross-linking centers, which facilitate curing, as well as synthetic polymers with recurring sulfobetaine units, such as for example Canadian Patent 7 74 054 are known.

As the image-receiving layer, conventionally known image-receiving layers can be used be used.

By using a pH reducing layer in one Recording material according to the invention can improve the stability increase the transmission image. Layers that reduce the pH value have proven to be particularly advantageous a reduction in the pH value in the image layer from about 13 or 14 to at least 11, preferably to 5 to 8 within a short period of time after the developing liquid has been received. To produce such a pH reducing agent Layers can be used, for example, acids made up of polymers, such as those in the USA patents 3,362,819, 2,584,030 and 2,548,575 and Belgian patent specification 603,747. Such from polymers Acids that have built up reduce the pH value of a recording material or an equivalent film unit after development. The polymers consist of polymers with acidic residues, for example Carboxylic acid residues and sulfonic acid residues, which with alkali metals, for example sodium and potassium, or with organic bases, in particular quaternary ammonium bases, for example Able to form tetramethylammonium hydroxide salts.

309825/0828

-jr-

The polymers can also provide potential acid groups Compounds contain, for example, anhydride or lactone groups or other groups which form with bases the same are able to react. The use of polymeric acids with free carboxyl groups has proven to be expedient, which are insoluble in water in the form of the free acid and which form water-soluble sodium and / or potassium salts. Examples for such polymeric acids are dibasic, acid half-ester derivatives of cellulose, i.e. derivatives with free carboxyl groups, for example cellulose acetate hydrogen phthalate, cellulose acetate hydrogen glutarate, Cellulose acetate hydrogen succinate, ethyl cellulose hydrogen succinate, ethyl cellulose acetate hydrogen succinate, Cellulose acetate succinate hydrogen phthalate, ether and ester derivatives of cellulose, modified with sulfoanhydrides, e.g. with ortho-sulfobenzoic anhydride, polystyrene sulfonic acids, Carboxymethyl cellulose, polyvinyl hydrogen phthalate, polyvinyl acetate hydrogen phthalate, Polyacrylic acid, acetals of polyvinyl alcohol with carboxy- or sulfo-substituted aldehydes, for example o-, m- or p-benzaldehyde sulfonic acid or o-, m- or p-Benzaldehydcarboxylic acid, also partial esters of ethylene-maleic anhydride copolymers, Partial esters of methyl vinyl ether-maleic anhydride copolymers and the same.

Furthermore, solid monomeric acidic substances, for example, can also be used to produce the layers under normal conditions Acids such as palmitic acid, oxalic acid, sebacic acid, hydrocinnamic acid, metanilic acid, p-toluenesulfonic acid, and benzene disulfonic acid be used. Others suitable for making the layers Compounds are disclosed in U.S. Patents 3,422,075 and 2 6.35 048.

Q 9 8.2t / 0 6 2-8

2250194

The layer reducing the pH value advantageously has a layer thickness of about 0.00762 to 0.038 mm, it can advantageously in the receiving part of the recording material or the film unit are arranged between the support and the image receiving layer, but also elsewhere, as long as it is able to fulfill the function of a layer which reduces the pH value in an effective manner.

A so-called timer or delay layer can advantageously also be placed over the layer which reduces the pH value be arranged, which has the task of reducing the pH to retard or control, as a function of the rate at which the alkali diffuses through the inert layer. Such a timer or delay layer can also be effectively used to prevent oxidizing compounds in a layer adjacent to the image receiving layer from which they are set free after the alkali breakdown of the timer layer.

Examples of such timer or delay layers can be made up, for example, of gelatin or polyvinyl alcohol or other polymers such as are described, for example, in US Pat. No. 3,455. Such timer or delay layers can further compensate for the different reaction rates within a wide temperature range, ie for example prevent a premature pH reduction if the action of the developing liquid b; i takes place at temperatures above room temperature, for example at temperatures from 35 to 38 ^° C.

Such retardation layers preferably have a layer thickness from about 0.00254 to 0.018 mm. Particularly advantageous results are usually obtained when producing of the retardation layers a hydrolyzable polymer or a

'$ 09825/0820

-pt-

Mixture of such polymers is used that or the slowly hydrolyzed by the developing liquid. Examples of such hydrolyzable polymers are polyvinyl acetate, Polyamides and cellulose esters.

Those for developing the recording materials according to the invention The developing liquids used are customary aqueous ones alkaline solutions of at least one alkaline compound, for example solutions of sodium hydroxide, sodium carbonate or an amine, for example diethylamine. The developing liquids preferably have a pH of above 12 and preferably they contain a developer compound of the type described. Such developing liquids advantageously contain them also a viscosity-increasing compound, for example a high molecular weight polymer, for example a water-soluble ether which is inert towards alkaline solutions, for example hydroxyethyl cellulose or an alkali metal salt the carboxymethyl cellulose, e.g., sodium carboxymethyl cellulose. Advantageously, such viscosity-increasing Compounds used in concentrations of from about 1 to about 5% by weight, based on the weight of the developing liquid, so that viscosities of about 100 to about 200,000 cps are achieved. If necessary, the developing liquids Adhesives or adhesive compounds are added, which the adhesion of the transparent cover sheet to the enlarge the photosensitive part of the recording material after development.

Does the alkaline developing liquid used to develop the recording material contain an auxiliary developing agent or an accelerating developing agent which does not correspond to the formula (OC) -D, this auxiliary developing agent can be used for example consist of p-methylaminophenol. 2, 4-diaminophenol,

'.! 098, ^ / 0828

p-Benzylaminophenol, Hydroquinone, Toluhydroquinone, Phenylhydroquinone, 4-methylphenylhydroquinone, i-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethylpyrazolidone and the same.

Furthermore, a wide variety of auxiliary developer connections, for example and accelerating developing agents of the type disclosed in U.S. Patent 3,039,869 can be used. In addition to the developing liquid, such developer compounds can optionally also, at least partially, in one or more layers of the recording material, for example in one or more silver halide emulsion layers, in layers in which the image dye-forming compounds be accommodated, in intermediate layers or in the image receiving layer.

If necessary, it can be of particular advantage to do a slow To use diffusing auxiliary developing agent and to accommodate them in an advantageous manner in the splittable container. Preferably such an auxiliary developer compound consists of one Silver halide developing agent that does not undergo a redox reaction after oxidation enters into or reacts with the oxichromogenic developer compounds. A typical utility developer link this The type is, for example, the 5,6,7,8-tetrahydro-5,8-methano-1,4-naphthalenediol.

The alkaline developing solutions used for developing the recording material according to the invention can also be used optionally contain a desensitizing agent, for example methylene blue or one substituted by a nitro radical heterocyclic compound or a 4,4'-bipyridinium salt to ensure that the light-sensitive material is no longer exposed if, for example, it is removed from a camera in which the recording material is being developed by splitting of the container containing the developing liquid became.

JÜ9825 / 0828

2280194

Although the alkaline developing liquid is advantageously accommodated in a splittable container, the Developing liquid into the recording material in another way or the film unit can be inserted, for example, by injecting the developing liquid with the aid of communicating Limbs, similar to hypodermic syringes, attached to either a camera or a camera cartridge can be arranged or attached, as for example from the USA patent 3 352 674 is known.

In addition, customary known opacifying agents or opacifying agents can be used to prepare the developing liquids, as long as they only have the desired opacity Bring light or opacity. Examples of suitable opacifying agents or opacifying agents are Barium sulfate, tin oxide, barium stearate, silver flakes, silicates, Aluminum oxide, zirconium oxide, zirconium acetylacetate, sodium zirconium sulfate, Kaolin, mica, titanium dioxide and organic dyes, for example of the nigrosine type and mixtures of various opacifiers. The concentration of the opacifier used should be sufficient for further exposure the light-sensitive layer or light-sensitive layers of the recording material by room or daylight through the transparent cover sheet after the development liquid has been distributed to avoid between the cover sheet and the underlying layers.

For example, there can be sufficient opacity or light impermeability with developing liquids that contain carbon black or titanium dioxide in concentrations of about 5 to 40 wt contain.

After the developing liquid with the opacifier in the recording material, or the film unit has been distributed, the further development of the recording material can also

30982 6 / 002.8. "

half of a camera in the presence of actinic radiation, with a view to the fact that the light-sensitive Layer or light-sensitive layers are adequately protected against the effects of incident radiation. One surface of the material is protected by the developing liquid containing an opacifier and the other main side by the opaque layer which is permeable to alkaline solutions.

Optionally, light-impermeable adhesive strips can be used to seal the edges of the recording material in front of the Protect entry of actinic radiation.

Use titanium dioxide or other white pigments as opacifiers used in the developing liquid, it may also be advantageous to use it together with a pH-sensitive, opaque dye, for example a phthalein dye. Such dyes are light absorbent or at the pH at which a Imaging occurs, colored and colorless or non-light absorbing at a lower pH. Further details regarding Such dyes which make opaque or make it opaque to light emerge, for example, from French patent specification 2,026,927.

The light-reflecting layer of the recording material which is permeable, opaque or light-impermeable for alkaline solutions can be made up of any of the opacifiers described and a binder in which the opacifier is dispersed be. White light-reflecting layers have proven to be particularly advantageous, as these provide an aesthetically pleasing background on which the Transmission image can be viewed, and wtil further the like layers that have optical properties that are desired for the reflection of incident radiation These light-reflecting layers can thus act as opacification

2250T94

medium for example also titanium dioxide, barium sulfate, zinc oxide, Barium stearate, silver flakes, silicates, aluminum oxide, Zirconium oxide, zirconium acetylacetate, sodium zirconium sulfate, kaolin, Mica or mixtures thereof can be used depending on the degree of opacity desired. To prepare the light reflecting Layers can be the usual known binders, which are permeable to alkaline solutions Provide layers, for example gelatin and polyvinyl alcohol.

Optionally, the light-reflecting layer can be customary optical brighteners are added, for example from stilbene, coumarin, triazine and oxazole.

If the opacity or opacity of the light-reflecting layer is to be increased, this can be dark-colored Opacifying compounds are added, for example carbon black and / or nigrosine dyes. Another method for There is an increase in the opacity or opacity capacity of the light-reflecting layers under the layer to arrange a special opaque or light-impermeable layer. This layer can for example consist of a dispersion of carbon black and / or a nigrosine dye in a permeable to alkaline solutions polymeric binders, such as gelatin or polyvinyl alcohol. Such an opaque layer is more expedient Have a density of at least 4, preferably a density of more than 7, and is opaque or impermeable to actinic radiation. The opaque or light-impermeable layer can further be combined with a developer trapping layer, if such is used. The light-reflecting and opaque layers advantageously have a thickness of approximately 0.0254 to 0.152 mm on. Of course, the layer thicknesses of these layers can also be outside the specified range, depending on the situation opacifiers used, the degree of opacity desired, and the like.

2200194

- Il

The transparent cover sheet can be any transparent one Material exist as long as the photographic properties of the recording material or the film unit through the cover sheet are not disadvantaged and as long as it is dimensionally stable. Typical flexible cover sheets permeable to actinic radiation can, for example, be made from films made from cellulose nitrate, Cellulose acetate, polyvinyl acetals, polystyrene, polyethylene terephthalate, Polycarbonates, poly-ot-olefins, e.g. polyethylene or polypropylene and other resinous polymers, as well as glass. The transparent ones are advantageous Cover sheets 0.05 to 0.152 mm thick. Advantageously, they can contain a UV absorber for exposure control. The cover sheet can optionally also have an adhesive layer which is activated by the alkaline developing liquid can be used to increase the adhesion of the cover sheet to the photosensitive part of the recording material.

The support of the recording material according to the invention can consist of one of the usual transparent supports. Optionally, the support may contain an ultraviolet radiation absorbing compound in order to produce dye images protect from fading by exposure to ultraviolet light.

Preferably, the photosensitive substances consist of the photosensitive ones Layer or photosensitive layers of the recording material of the invention composed of a silver halide. That Silver halide can be made from any of the customary used for the production of the photographic recording materials Consist of silver halide, for example silver chloride, silver bromide » Silver bromide iodide or silver chlorobromide iodide or mixtures of this. Coarse-grain and fine-grain silver halide emulsions can be used to prepare the recording materials which can be prepared by customary known methods, for example single enema emulsions, double enema emulsions,

309 82S / 082 8

2290194

e.g. Lippmann emulsions and ammoniacal emulsions as well as in Emulsions ripened in the presence of thiocyanates or thioethers, as described, for example, in US Pat. 3 320 069 and 3 271 157 are described in more detail. For the production of the recording materials can furthermore be surface-forming emulsions or internal image or internal grain emulsions are used, as for example in US Patents 2,592,250, 3 206 313 and 3 447 927 are described in more detail. With the emulsions it can also be, for example, emulsions with regular silver halide grains, such as, for example in the journal J. Phot. Be., Volume 12, No. 5, from September / October 1964, on pages 242 to 251 are described in more detail. Optionally, for the production of the recording materials Mixtures of surface-forming emulsions and inner-grain or inner-image emulsions can also be used, as for example in U.S. Patent 2,996,382.

In addition, for the production of the recording materials Negative type emulsions as well as direct positive emulsions can be used, such as those in the United States patents 2,184 Q13, 2,541,472, 3,367,778, 3,501,307, 2,563,785, 2,456,953 and 2,861,885, British Patent 723 019 and Den. Belgian Patents 780 538, 780 539 and 780 540 as well as the USA patent applications with the serial no. 154 154, 154 155 and 154 224, in each case from June 17, 1971 to be described in more detail.

In a particularly advantageous manner, they are exposed imagewise Photographic recording materials according to the invention in the presence of a development inhibitor which releases them Connection developed. Such compounds can be in a or more layers of the recording material are accommodated in contact with the syllable halide emulsion layer or layers. On the other hand, such development inhibitors can release compounds but also alkaline ones

9326/0828

Developing liquid are applied in which In the case of diffusing development inhibitors liberating compounds can be used. In a particularly advantageous way can release compounds that release development inhibitors those composed of a mercaptan development inhibitor can be used free-setting hydroquinone exist. Typical compounds of this type are, for example, from the USA patents 3,379,529 and 3,364,022 known. Such development inhibitors can advantageously liberate them or splitting off compounds in one or more layers of a recording material in concentrations of 2 to about 200 mg, especially in concentrations of about 5 to about 75 mg

2
can be accommodated per 0.0929 m of support surface. A particularly advantageous compound which splits off a development inhibitor or releases it is, for example, 2,3-dimethyl-o- (1-pheny1-5-tetrazoylthiohydroquinone.

In general, when using photographic recording materials of the type described positive image recordings in the image receiving layer by pickling the diffusing image-forming compounds which have not been immobilized or non-diffusing in the photosensitive part of the recording material stay behind, received. It should also be noted that the photosensitive part of the recording material has an image recording which can be useful. For example, the mobile or diffusing substances after exposure and development are washed off to produce a negative image record, for example one Archive negatives. On the other hand, there may be the silver halide emulsions can also be selected such that a positive image recording in the photosensitive part of the recording material takes place, for example, by using one or more reverse or direct-positive silver halide emulsions,

3Ü982S / Ö828

The following examples are intended to illustrate the invention in more detail .

The following examples 1 and 2 show that certain, preferably used compounds of the invention (with reduced azomethine groups) a) produce colorless layers _ΰ when they are made into layers, for example using gelatin or another hydrophilic binder, b) are oxidized to indophenols can and c) after oxidation by contact with a mordant can be converted into an image dye with desirable spectral properties »

example 1

A) First of all, a conventional coating device was used on a support a layer of 300 mg gelatin, 50 mg of compound I and 150 mg diethyl lauramide, each per 0.0929 m Applied to the support surface. The layer turned out to be practically colorless. The layer was then examined spectrophotometrically. The sensitometric values obtained thereby are as follows Table 1 listed. The absorption curve of the compound Ϊ is also shown in curve A in Figure 1,

B) A section of the recording material obtained was _{immersed for 30 seconds in an aqueous neutral (pH = 7 s} 0) oxidizing solution of K, Fe (CN) ^ at room temperature and then dried. The layer turned orange-yellow. This material was also examined spectrophotometrically. The results obtained are; in the following table! compiled. The absorption curve of the obtained indophenol is represented by curve B in FIG. 1 shown.

C) A third sample of the material described under A) was immersed in an aqueous solution of hexadecyltrimethylammonium bromide with a value of 7.0 and dried in this way

obtained a blue-green layer. The discoloration of the layer from colorless to blue-green became quite evident from air oxidation and brought about simultaneous or subsequent contact of the compound I with the pickling agent. The sensitometric measurements of this material are compiled in Table 1 below. The absorption curve of the cyan dye obtained is in Figure 1 represented by curve C. / "

Table 1

Curve treatment Xmax (nm). D _mQV

JIl CtA

none none pronounced 0.08

Point in the visible area

BK ₃ Fe (CN) ₆ 472 0.34

C aqueous solution of hexa- 625 1.08

decyltrimethylammonium bromide, pH = 7.0
(Air oxidation)

Example 2

A) First, a layer was applied by hand to a layer support from 300 mg gelatin, 50 mg of compound II and 150 mg diethyl lauramide, each applied per 0.0929 m of support surface. The material obtained was then tested spectrophotometrically. The layer turned out to be colorless. The quantitative sensitometric test results obtained are as follows Table 2 compiled. The absorption curve of the compound II is represented by curve A in FIG.

/ (Pie substrates passed here and in the examples below made of cellulose acetate).

3 0 9 8 2 S / 0 8 2 8

B) A section of the material described under A) was immersed for 30 seconds in an aqueous neutral (pH = 7.0) oxidizing solution of K-Fe (CN) ₆ at room temperature and then dried. In this way an orange-yellow layer was obtained. The sensitometric values of this layer are listed in Table 2. The absorption curve of the indophenol dye produced in the manner described is shown by curve B in FIG.

C) A section of the material treated as described under B) was immersed in an aqueous solution of hexadecyltrimethylammonium bromide for 30 seconds a pH of 12 and room temperature, then washed and dried. In this way a blue-green layer was obtained. In this case the more complete oxidation of the originally colorless compound is through KgFe (CN) g (as opposed to partial oxidation by air, see them during the procedure described in Example 3) is likely a factor in the subsequent creation of the final blue-green dye with a higher extinction coefficient. Treatment with the aqueous solution of hexadecyltrimethylammonium bromide at the higher pH (12.0 versus 7.0) may also be of importance in producing the higher dye density be. The sensitometric measured values obtained are shown in Table 2 below. The absorption curve of the cyan dye obtained is shown by curve C in Figure.

3Ü982S / 0828

2250194

Tabel

Curve

treatment

no

K ₃ Fe (CN) ₆

K ₃ Fe (CN) ₆ (Plus aqueous solution of hexadecyltrimethylammonium bromide, pH> 12)

Max

Max

none out
embossed tip
in the visible
area O , 12 485 O , 40 636 2 , 08

Example 3

This example illustrates the transmission of an inherently colorless oxichromogenic developer compound on four image-receiving layers, each with a different mordant. The oxidation the oxichromogenic developer compound with formation of the corresponding dye took place by air oxidation Separating the developing agent-containing materials from the image-receiving elements.

A) A section of that described in Example 2 under Section A) Compound II material was contacted for 30 seconds with an image receiving element, which contained polyvinylpyridine as a mordant in the image receiving layer. The contact took place in the presence of a viscous developing liquid consisting of a solution of KOII and hydroxyethyl cellulose in water. After the test specimen had been separated from the image receiving element, the latter was washed with water for 3 minutes.

2260114

B) The procedure described in section A) was repeated, but this time an image-receiving element was used which was a coacervate mordant of N-n-hexadecyl-N-morpholinium ethosul- * fat and methyl tri-n-dodecylammonium-p.-toluenesulfonate.

C) The procedure described in section A) was repeated, wherein but this time an image-receiving element was used which, as a mordant, was copoly / styrene- (NjN-dimethyl-N-beazyl-N-S-maleimidopropyl) ammonium chloride_7 contained.

D) The procedure described in section A) was repeated " with the exception, however, that this time an image receiving element is used was used as a mordant N-n-octadecyl-tri-butylamisonium bromide contained.

In all four cases, intense deep blue-green image-receiving layers became obtained after separating the image receiving elements from the specimens. The dyes of the layers became whole Obviously obtained by air oxidation and the reaction between oxidized dye and mordant. The shades of the individual blue-green images differed somewhat when viewed visually due to the different nature of the individual mordants used in the manufacture of the image receiving elements were used.

Example 4

A multilayer photographic recording material was produced by applying to a layer support (the concentration data given below relate to a layer support area of Ο _? Ο929 m ² ):

1.) a layer of 300 "mg gelatin, 50 mg of compound II and 150 mg of diethyl lauramide;

9 8.2

2200194

2) a silver halide emulsion layer containing 250 mg of gelatin and 200 mg of silver and

3) a gelatin layer of 80 mg gelatin.

A sample of the prepared recording material was then made in a sensitometer through a test object with graduated density levels exposed and then for 1 minute with an image-receiving element with N-n-octadecyl-tri-butylammonium bromide in the image-receiving layer brought into intimate contact in the presence of a viscous developing liquid. The development fluid possessed the following composition:

NaOH 20 g

1-phenyl-4-methy1-4-hydroxymethy1-3-

pyrazolidone 0.75 g

Hydroxyethyl cellulose 25 g

made up to 1 liter with water
pH value ■ 13.7.

After separation of the light-sensitive material from the image-receiving element, the latter became a well-defined one blue-green positive image of the test object visible.

Example 5

Was prepared nin another recording material of the type described in Example 4, except that this time the lowermost layer, that is, the I layer of the carrier layer closest to the compound in place of compound II contained. Visual inspection of the recording material showed that it did not differ from a corresponding material which did not contain any oxichromogenic developing agent, since the oxichromogenic developing chlorine compound is practically colorless. Only the yellow-brownish tone of the silver halide emulsion layer was visible.

3 0 9 8 ^ / 0828

A second sample of the material was subjected to a bleaching test for 1 week in which the test specimen was subjected to a 2O ^? digen relative humidity was exposed to a temperature of 49 C. Under these conditions, the color of the material changed only slightly to brown-yellow. It follows from this that the oxichromogenic developer compounds used according to the invention are relatively stable developer compounds, ie. oxidation-resistant compounds and that thus recording materials with such. Compounds can be kept for long periods of time before development.

Example 6

Another multilayer photographic recording material was produced by applying the following layers to a layer support (the following concentration data again relate to a layer support area of around 0.0929 m ² ):

1) a layer of 300 mg of gelatin, 50 mg of compound II and 150 mg of diethyl lauramide;

2) a silver halide emulsion layer of 100 mg silver, 250 mg Gelatin and 10 mg of i-phenyl-3-pyrazolidone;

3) a gelatin layer of 80 mg gelatin.

A sample of the produced recording material was in a Sensitometer through a test object with graduated density levels exposed and then brought into intimate contact with an image receiving element for 30 seconds. The mordant of the image receiving layer of the image receiving element consisted of N-n-octadecyl-tfributylammonium bromide. The contacting took place in the presence of a viscous developing liquid of the following composition:

309825/0828

NaOH 20 g

1-phenyl-4-methyl-4-hydroxymethyl-3-

pyrazolidone 0.75 g

Hydroxyethyl cellulose 25 g

made up to 1 liter with water
pH - 13.7

After separating the two elements, the image receiving layer of the image receiving element a well-defined blue-green colored positive image of the test object is visible. By incorporating a Auxiliary developing agent in the photosensitive layer (in addition to the use of a corresponding compound in the Developing fluid) was an image of desirable sensitometric Properties and improved incubation properties obtained.

Example 7

The procedure described in Example 6 was repeated except that this time a developing liquid was used which was was obtained by dissolving 40 g of KOH and 25 g of hydroxyethyl cellulose in 1 liter of water. It became a picture more appropriate Maintain quality.

Example 8

The procedure described in Example 6 was repeated, wherein however, this time two different image receiving elements were used. The image-receiving elements contained a coacervate of N-n-hexadecyl-N-morpholinium ethosulfate and methyltri-n-dodecylammonium p-toluenesulfonate as a mordant and on the other hand copoly- / "styrene- (N, N-dimethyl-N-benzyl-N-3-maleimidopropyl) ammonium chloride_7" Results corresponding to those described in Example 6 were obtained.

309826/0828

2260154

-yf- U

Example 9

There were other recording materials A, B and C as in example 1, with the exception, however, that the compound III was used instead of the compound I.

A) This material was produced by applying a layer of 300 mg gelatin, 50 mg of the compound III and 150 mg of diethyl lauramide, each per

2
0.0929 m of support area were applied. The material was then tested in a spectrophotometric manner. The measurement results obtained are summarized in Table 3 below. The absorption curve of compound III is shown by curve A in FIG.

B) A section of the material described under A) was immersed for 30 seconds in an aqueous (pH = 7.0) neutral oxidizing solution of K, Fe (CN) ₆ at room temperature and then dried. A purple layer was obtained. The sensitometric data of this layer are also contained in Table 3 below. The absorption curve of the indophenol dye obtained is the. Curve B in Figure 3.

C) Another section of the material described under A) was in an aqueous solution of Cetyltrimethylanunoniumbromid with immersed to pH 7.0 and then dried. A distinctly purple-red layer was obtained. The overpass The originally colorless layer in a purple-red layer is based on an air oxidation and a simultaneous one or subsequent contact of the compound III with the mordant, i.e. in the present case an aqueous solution of Cetyltrimethylammonium bromide. The sensitometric values of these Layer are also listed in Table 3 below. The absorption curve of the generated magenta image dye is the Curve C of figure 3. ■

309625/0 «28

Table 3

Curve treatment

λmax (nm. ) D. Max weak tip
green area
Spectrum in the
of O , 29 527 1 , 82 537 2 , 36

without

BK ₃ Fe (CN) ₆

C aqueous solution of cetyltrimethylammonium bromide
(Air oxidation)

The procedure described in Example 3 was repeated with the Except, however, that this time the practically colorless oxichromogenic developer compound III was used. Oxidation of the oxichromogenic Developer connection was carried out by air oxidation after separation of the corresponding layers containing the compound from the image receiving layer.

After a 30 second contact of the oxichromogenic developer compounds containing layers with the image-receiving layers, the image-receiving layers were washed with water for 3 minutes washed.

In all four cases, crimson-colored image-receiving layers became good quality, the hues of the layers depending on differ slightly from each other of the individual dressings used.

Example 11

First, a photosensitive pliotographic recording material was made produced by applying them to a layer support (the following concentration data relate in each case to on a substrate surface of 0.0929 m):

3098 ^ 6/0828

1) a layer of 300 mg gelatin, 50 mg of compound III and 150 mg of diethyl lauramide;

2) a silver halide emulsion layer of 250 mg gelatin, 10 mg Silver and 10 mg of i-phenyl-3-pyrazolidone.

A portion of the recorded material produced would be in a sensitometer through a test object with graduated density levels exposed and then with an image-receiving layer for 1 minute with N-n-octadecyl-tri-butylammonium bromide as a pickling agent contacted in the presence of a developing liquid. For the development became a development liquid of that in Example 4 specified composition is used.

After the recording material has been separated from the image-receiving layer a well-defined purple-red positive image of the test object became visible in the image-receiving layer *

Similar results xv were obtained when a recording material was used, which contained the compound IV instead of the compound III.

Example 12 ^f

Results corresponding to those described in Example 3 were then obtained obtained when transfers were made using image-receiving layers that acted as mordants either Coacervate of N-n-hexadecyl-N-morpholinium ethosulphate and methyl-trin-dodecylammonium-p-toluenesulphonate or from copoly / styrene (N, N-dimethyl-N-benzyl-N-3-maleiimidopropyl) ammonium chloride contained.

Example 13

First of all, it was applied to a layer support by means of a coating device a layer of 300 mg of gelatin, 50 mg of compound V and 100 mg of diethyl lauramide was applied. The applied layer turned out to be practically colorless.

30 9828/0828

Now there has been a photographic light-sensitive material produced by applying to a layer support (the following concentration data relate each on a substrate area of 0.0929 m):

1) a layer of 300 mg of gelatin, 50 mg of compound V and 100 mg of diethyl lauramide;

2) a silver halide emulsion layer of 250 mg gelatin, 10 mg i-phenyl-3-pyrazolidone and 100 mg silver;

3) a gelatin layer of 80 mg gelatin.

A first portion of the resulting recording material was exposed in a sensitometer through a test object with graduated density levels and then exposed for 30 seconds with an image-receiving layer brought into contact in the presence of the developing liquid described in Example 4. The image receiving layer contained a coacervate of N-n-hexadecyl-N-mörpholinium ethosulfate as a pickling agent and methyl tri-n-dodecylammonium-p-toluene sulfate.

A second section was run for 60 seconds in the presence of the developing liquid brought into contact with an image-receiving layer which contained polyvinylpyridine as a mordant.

A third section was held for 60 seconds in the presence of the developing liquid Brought into contact with an image receiving layer, the pickling agent N-n-octadecyl-tri-butylammonium bromide contained.

After separating the three recording materials from the image receiving elements Well-defined yellow-colored positive reproductions of the test object were obtained in each case.

309828/0828

-V-

Corresponding results were obtained when the experiments with compounds VI, VII and VIII were repeated.

Example 14

A) Using a coating device, a layer support was coated with a layer which contained 300 mg of gelatin, 55 mg of the stabilized compound IX and 50 mg of diethyl lauramide ^{per 0.0929 m 2 of support area.} The layer turned out to be clear and transparent. The layer was not colored in any way.

B) A section of the material obtained was immersed in a neutral (pH = 7.0) aqueous solution of K ₃ Fe (CN) _6. There was no change in color, ie no dye was produced.

The experiments described under A) and B) were repeated, wherein However, this time specimens were used which this time the non-stabilized developer instead of the stabilized oxichromogenic developer oxichromogenic developer contained.

When the results obtained were compared, it was found that less Soiling or discoloration occurred when recording materials were used with the stabilized oxichromogenic developer.

The stabilized oxichromogenic developer compounds have exhibits improved resistance to color development in a neutral environment, such as that of photographic recording materials prevails. Furthermore, they can be easily removed at the higher pH values used in image transfer processes predominantly convert so that they undergo chromogenic oxidation can.

30982 6/0828

- / ί ~ ta

While this example shows that the color developing agents are resistant to color generation at neutral pH values, can be seen from the following examples 15, 16 and 17 show that oxichromogenic dye developers are easy to apply in dyes at elevated pH values.

Example 15

A photographic light-sensitive material was produced by applying it to a layer support (the following concentration data relate in each case on a carrier area of 0.0929 m):

1) a layer of 300 mg of gelatin, 55 mg of compound DC and 50 mg of diethyl lauramide;

2) a negative silver halide emulsion layer composed of 250 mg gelatin, 100 mg silver and 10 mg 1-phenyl-3-pyrazolidone and

3) a gelatin layer of 80 mg gelatin.

A section of the recording material produced was passed through a test object with graduated density levels in a sensitometer exposed and then in contact with an image receiving material for 30 seconds in the presence of a viscous developing liquid brought, ias a pickling agent a coacervate of N-n-hexadecyl-N-morpholinium ethosulfate and methyl tri-n-dedecylammonium p-toluenesulfonate contained.

The developing liquid had the following composition:

KOH 20 g

Hydroxyethyl cellulose 25 g

made up to 1 liter with water
pH = 13.7.

After separating the exposed recording material from the image receiving element A well-defined blue-green positive image of the test object was shown in the image-receiving layer.

Example 16 .

The following layers were applied to a layer support (the following concentration data relate to a layer support area of 0.0929 m ² ):

1) a silver halide emulsion layer of 200 mg gelatin,

150 mg of silver, 50 mg of compound IX, 75 mg of diethyl lauramide and 10 mg of 1-phenyl-3-pyrazolidone and

2) a gelatin layer made of 80 mg GElatin *

A section of the recording material was exposed imagewise and then with an image receiving element and an entrickling liquid brought into contact as ^ described in example 15 * A blue-green positive image of excellent quality was obtained.

Example 17

The procedure described in Example 15 was repeated, but this time using an image-receiving element with an image-receiving layer which contained copoly / "styrenic (N, N-dimethyl-N-benzyl-N-3-maleiimidopropyl) ammonium _- 7 chloride as a mordant. Accordingly, favorable results as described in Example 15 and Example 16 were obtained.

Example 18

The procedure described in Example 15 was repeated, but this time using a recording material which is described in the layer closest to the support instead of the compound-IX the compound XXVl contained. There were corresponding

3ÜÖ82S / 0828

8fr

Results as described in Example 15 were obtained. Example 19

First, a photosensitive recording material was produced by applying the following layers to a conventional cellulose acetate film support (the concentration data given below relate to a support area of 0.0929 m ² ):

1) a red reactive silver bromide iodide emulsion layer containing 100 mg of Ag _1, 80 mg of the stabilized oxichromogenic dye developer compound IX, 120 mg of diethyl lauramide, 10 mg of i-phenyl-3-pyrazolidone and 125 mg of gelatin;

2) an intermediate layer of 250 mg gelatin, 70 mg 2, S-di-sec.-dodecylhydroquinone (see Belgian patent specification 763 752), 72 mg diethyllauramide and 75 mg 1- (2,4,6-trichlorophenyl) -3 - ^ * 3- (2,4-diamylphenoxyacetamido) benzamido_7-4- (4-methoxyphenylazo) - 5-pyrazolone as a yellow filter dye;

3) a green sensitive silver bromide iodide emulsion layer of 90 mg Ag, 45 mg of compound XII as a developer, 67 mg of diethyl lauramide, 9 mg of 1-phenyl-3-pyrazolidone and 100 mg of gelatin;

4} a top layer of 80 mg gelatin.

A second light-sensitive material was also used produced, which differed from the one described only in that the intermediate layer 195 mg of diethyl lauramide and an additional 50 mg of 2,3-dimethyl-6- (1-phenyl-5-tetrazolylthio) hydroquinone contained.

The two recording materials were exposed imagewise and developed by being in the presence of a developing liquid for 60 seconds in contact with an image receiving element

3 00826/0828

The image-receiving layer of which is hexadecyltrimethylammonium bromide as a mordant contained. The development liquid used consisted of a solution of 56 g of KOH and 32 g of hydroxyethyl cellulose in 1 liter of water.

The developing liquid became uniform between the recording materials and distributed to the image receiving elements. Bringing the photosensitive recording materials into contact with the image receiving elements was carried out by passing the sandwich formed through the gap formed by two rollers, i.e. an arrangement such as is used, for example, in self-development cameras for developing exposed recording materials is used.

After 60 seconds of contact, the Image-receiving layer developed only little visible image dye. However, a dense dye image was formed when the image-receiving layer Exposed to air for 3 to 5 seconds.

When using the recording material with the 2,3-dimethyl-6- (1-phenyl-5-tetrazolylthio) -hydroquinone in the interlayer was compared to the cyan dye image (i.e. in the blue and green exposure areas, which achieves better image density.

The two recording materials showed no loss of sensitivity compared to a comparison material, xielches contained no oxichromogenic developer compound as the oxichromogenic Developing compounds are not dyes, which absorb radiation to be considered in the visible range of the electromagnetic spectrum.

Example 20

In the case of multicolor image recording materials for diffusion transfer process is the blue sensitive silver halide emuls ions schiriit, which provide a golden dye with a

309825/0826

oxichromogenic compound is in contact, preferably such arranged that the other silver halide emulsion layers, which are in contact with oxichromogenic compounds, between the blue-sensitive emulsion layer and the image-receiving layer is arranged. Preferably for the production of such recording materials stabilized oxichromogenic developer compounds are used.

The layers specified in the following order were applied to a polyethylene terephthalate substrate of 0.10 mm (the following concentration data again relate to a substrate area of 0.0929m ² ):

1) a layer of 100 mg gelatin, 60 mg of compound XVIII,

90 mg of Ν, Ν-diethyl lauramide and 0.75 mg of bisvinylsulfonylmethyl ether;

2) a layer of 70 mg gelatin, 90 mg blue-sensitive silver halide, 10 mg of 1-phenyl-3-pyrazolidone and 0.52 mg of bis-vinylsulfonylmethyl ether;

3) a layer of 200 mg gelatin, 20 mg 2,5-di-sec-dodecylhydroquinone, 100 mg 1- (2,4,6-trichlorophenyl) -3 - / "* 3- (2, 4-di-

amylphenoxyacetamido) benzamido_7-4- (4-methoxyphenylazo) -5-pyrazolone and 1.5 mg bisvinylsulfonyl methyl ether;

4) a layer of 170 mg gelatin, 50 mg green sensitive silver, 50 mg of the compound XV, 75 mg of Ν, Ν-diethyllauramide, 10 mg of 1-phenyl-3-pyrazolidone and 1.3 mg bisvinylsulfonyl methyl ether;

5) a layer of 200 mg of gelatin, 20 mg of 2, 5-di-sect-Dodecylhydiochinon, 30 mg of 1- (2,4,6-trichlorophenyl) -3- / ~ OT (3-pentadecylphenoxy) butyramido_7benzamido-5- pyrazolone, coupled with oxidized 4-amino-3-methyl-N-ethyl-K- f »- (nethanesulfonamido) ethyl-

3üü «26 / 0ft? 8

-ff- 93

aniline, 1.5 mg bis-vinylsulfonylmethyl ether and 25 mg 2,3-dimethyl-6- (1-phenyl-5-tetrazolylthio) hydroquinone;

6) a layer of 195 mg gelatin, 60 mg red-sensitive silver halide, 50 mg of the compound IX, 75 mg of Ν, Ν-diethyllauramide, 10 mg of 1-phenyl-3-pyrazolidone and 1.5 mg of bis-vinylsulfonylmethyl ether as

7) a layer of 70 mg gelatin.

The light-sensitive material obtained was then imagewise exposed through the support and developed by being exposed for 60 seconds in the presence of a developing liquid with an image receiving element as described in Example 3 (D) was brought into contact. The developing liquid used was made by dissolving 56 g of KOH and 32 g of hydroxyethyl cellulose obtained in 1 liter of water. The developing liquid became uniform between the image recording material and the image receiving layer distributed as the sandwich formed from the recording material and the image-receiving element by that of two pressure rollers formed gap, as it is used in a self-development camera, was performed.

After about 60 seconds of contact was. in the image receiving layer very little visible dye image recognizable. After the image receiving element of exposure however, after exposure to air, a three-color dense dye image was formed in the image-receiving layer.

It was found that the diffusion time required for the transfer process, i.e. the time it takes for an image dye to produce Connection for transmission in the image receiving layer required, was less than the time required when dye developer / in a special layer under the SiI

of the state of the art

309825/0828

Berhalide emulsion layer housed with respect to the exposure side will.

Example 21

This example describes the production of a particularly advantageous one A recording material of the invention in which the image-receiving layer is applied with the photosensitive layers on one and the same support.

A transparent 0.010 cm thick polyethylene terephthalate substrate was coated with the layers specified below in the order specified below (the following concentration data again relate to a substrate area of 0.0929 m ² ):

1) an image receiving layer made of a coacervate of 22 mg of methyl tri-n-dodecylammonium-p-toluenesulfonate and 150 mg of N-n-hexyldecyl-N-morpholinium ethosulfate and 743 mg of gelatin;

2) a layer of 300 mg gelatin, 3000 mg TiO ₂ and 1.3 mg bisvinylsulfonyl methyl ether;

3) a layer of 360 mg gelatin, 300 mg carbon black and 1.3 mg bisvinylsulfonyl methyl ether;

4) a release liner of 500 mg uncured polyvinyl alcohol;

5) a layer corresponding to layer 6 of example 20;

6) a layer corresponding to layer 5 of example 20;

7) a layer corresponding to layer 4 of example 20; .

2160194

- f-

8) a layer corresponding to layer 3 of example 20;

9) a layer corresponding to layer 2 of example 20;

10) a layer corresponding to layer 1 of example 20 and

11) a gelatin top layer of 70 mg gelatin.

A 0.010 cm thick polyester cover sheet was then applied to the gelatin cover layer 11, whereupon between the cover sheet and the recording material a rupturable container, the content of which was made from a developing liquid of that given in Example 20, was brought Composition consisted of additional per liter of solution still contained 10 g of soot. The film unit produced in this way was then exposed imagewise through the transparent cover sheet, whereupon the film unit through the stack of two Rolling gap formed was guided, whereby the splittable container split open and its contents between cover sheet and recording material was distributed. After the developing liquid was distributed, the film unit was soaked for 60 minutes exposed to room light. The support with the image-receiving layer was then attached to the light-sensitive layers the stripping layer separated. After about 3 to 5 seconds it had a dense three-color image was formed in the image-receiving layer which could be viewed through the support. The stripping layer can also be omitted, i.e. the individual Parts of the film unit can also stay together if a Oxidizing agent is present in the image receiving layer. For example, images of excellent quality will then be obtained without stripping obtained in the image receiving layer if 100 mg 1,4-didecyl-1,4-diazabicyclo- / ~ 2,2,27octanoniumpersulfat, dissolved in dibutyl phthalate with the e.g. from a coacervate existing pickling agents are available.

The recording materials advantageously have an acidic layer for reducing the pH value after development in particular when there is no separation of the image receiving part, i.e. when the individual parts of the film unit stay together.

For example, polyacrylic acid is advantageously suitable for producing acidic layers. So can in an advantageous manner for example a cover sheet with a polyacrylic acid layer and a delay or timer layer made of polyvinyl acetate the polyacrylic acid layer can be used. The acidic layer then turns the individual layers of the recording material into the same order in which it is neutralized by the developing liquid activated.

If appropriate, it can also have a splittable container or others Means can be used to bring an oxidizing agent into contact with the image receiving layer after exposure of the film unit. Furthermore, it is also possible to use a transparent, porous support with the image receiving layer, so that a sufficient amount of air can enter and allow chromogenic oxidation of the oxichromogenic compounds.

In a particularly advantageous manner, however, an oxidizing agent is used in the image-receiving layer, this oxidizing agent preferably consists of a compound which is unable to diffuse into the light-sensitive layers.

Example 22

This example illustrates the ear trap of compound XVIJI in an image receiving layer, which acts as an irritant, N-n-octadecyl-tributylammonium bromide contains.

r.s another material was prepared according to Pci spie] 2 (A), where but this time instead of compound II, compound XVlII uses wuide. The layer u; n tiufjiotrapene on the substrate

^ (J 9 Ö 2 & / OB / M

BAD ORtGJHAi.

practically colorless. The quantitative sensitometric measurements result from curve A in FIG. 4.

The produced material was then treated with the for 30 seconds Rild receiving element brought into contact, in the presence a viscous developing liquid made from KOH and hydroxyethyl cellulose in water. A dense yellow dye image was formed 3 to 5 seconds after the layer was separated from the image-receiving layer obtain. The absorption characteristics of the dye result from curve C in FIG. 4,

Example 23

This example illustrates the image-wise transfer of the oxichromogenic Developer compound XII from an exposed photographic material having a single silver halide emulsion layer onto an image receiving layer during the development process. The example further illustrates the chromogenic oxidation of the compound to a dye during of the development process.

A) First, a photosensitive recording material was produced by applying the layers listed below to a transparent layer support (the concentration data given below relate in each case to a layer support area of 0.0929 m ² ):

1;) a layer of 125 mg gelatin, 75 mg bioethyl lauramide and 50 mg of the stabilized oxichromogenic developer compound of example 1;

2) a silver halide emulsion layer containing 100 mg gelatin, 100 mg Silver and 10 mg of 1-phenyl-3-pyrazolidone;

3Q982S / 0828

3) a layer of 80 mg gelatin.

B) A section of the recording material described under A) was exposed through a test object with graduated non-steps. A 0.010 cm thick was then placed on the exposed material A layer of a developing liquid of the following composition is applied:

KOH 40 g / L

Hydroxyethyl cellulose 30 g / L
pH - 13.7.

Immediately after application of the developing liquid, was an image-receiving element having an image-receiving layer applied thereon, which consists of a gelatin layer with N-n-octadecyltributylammonium bromide duration.

After a contact time of 1 minute, the image-receiving element was separated. The image receiving layer showed a well-defined purple-red positive image of the test object.

Example 24

The process described in Example 23 was repeated, but this time using a recording material which, instead of 50 mg of compound XII, contained 40 mg of oxichromogenic developer compound XVII per 0.0929 m ^{2 of} support surface. After image-appropriate exposure and development as described in Example 23, a well-defined yellow positive image of the test object was visible in the image-receiving layer of the image-receiving element.

309828/0828

Example 25

First of all, a so-called integrated recording material was used for the Color transfer process produced by placing the following on a transparent polyethylene terephthalate layer carrier Layers were applied in the order given below (the following concentration data relate to each on a substrate area of 0.0929 m):

1) an image receiving layer made of 100 mg gelatin, 200 mg copoly- / ~ styrene / N-benzyl-N, N-dimethyl-N- (3-maleimidopropyl) aminonium chloride and 200 mg of a nitroxy oxidant of the following formula:

NH-CO-CH ₂ -O

^C 5 ^H 11

2) a layer of 200 mg gelatin and 2000 mg titanium dioxide;

3) a layer of 156 mg gelatin and 250 mg carbon black as an opacifier or opacifying agent;

4) a layer of 75 mg gelatin, 70 mg 2,5-di-sec-dodecylhydroquinone and 23 mg tricresyl phosphate;

5) a red sensitive silver bromide iodide emulsion layer at 70 mg Silver j 230 mg gelatine, 42 mg of the

ä09825 / 0828

benen compound X, dispersed in 73 mg of diethyl lauramide, 5 mg 5- (2-Cyanoethylthio) -1-phenyltetrazole, dispersed in 15 mg tricresyl phosphate and 10 mg of 5,6,7,8-tetrahydro-5,8-methano-1,4-naphthalenediol;

6) a layer of 300 mg gelatin, 70 mg 2,5-di-sec-dodecylhydroquinone and 30 mg of a magenta filter dye of layer 5 of Example 20, dissolved in 50 mg of diethyl lauramide;

7) a green sensitive silver bromide iodide emulsion layer with

70 mg of silver, 2 30 mg of gelatin, 54 mg of compound XV, dispersed in 64 mg of diethyl lauramide, 5 mg of 5- (2-cyanoethylthio) -1-phenyltetrazole, dispersed in tricresyl phosphate and 10 mg 5,6,7,8-tetrahydro-5,8-methano-1,4-naphthalenediol;

8) a layer of 300 mg gelatin, 70 mg 2,5-di-sec-dodecylhy-

droquinone and 100 mg of the yellow filter dye of layer 3 from Example 20, dispersed in 28 mg of diethyl lauramide;

9) a blue sensitive silver bromide iodide emulsion layer at 70 mg Silver, 210 mg gelatin, 64 mg of compound XXIV, dispersed in 106 mg diethyl lauramide, 5 mg 5- (2-cyanoethylthio) -1-phenyltetrazole, dispersed in 15 mg tricresyl phosphate and 10 mg 5,6,7,8-tetrahydro-5,8-methano-1,4-naphthalenediol and

10) a layer of 50 mg gelatin.

A transparent cover sheet was also used for the described Recording material produced in that on a transparent Polyethylene terephthalate film base the following layers were applied (the following concentration data relate to again on a substrate surface of 0.0929 m):

1) a layer of 900 mg gelatin, 900 mg polyacrylic acid and 760 mg Imidazole;

£ 30982/0 8 7 8

2) a layer of 1140 mg cellulose acetate and 60 mg of a copolymer from styrene and maleic anhydride,

The photographic material produced first became a multicolored test object with graduated density levels exposed, whereupon the transparent cover sheet was applied to the recording material and whereupon a splittable A container with a developing liquid containing an opacifying agent is placed between the recording material and the cover sheet became. The sandwich formed from the recording material, the separable container and the cover sheet was then stacked by the two arranged rollers formed gap with a width of 0.20 mm out. In doing so, the splittable container was split open, like this that the contents of the container could be distributed between the cover sheet and light-sensitive recording material *

The developing liquid used had the following composition on:

g / L

Potassium hydroxide 51

Hydroxyethyl cellulose 30

Potassium bromide 40

α-Benzyl picolinium bromide 15

jjjyj-i, 4- naphthalenedlol 15

Soot - - 40

After about 1 to 2 minutes, the recording material became at Viewing through the transparent layer support of the laaterials a well-defined color image of the original is visible.

The nitroxyl oxidizing agent used to produce the recording material was obtained by reacting the acyl chloride containing the corresponding ballast groups with 4-amino-2,2,6,6-tetramethyl piperidin-1-oxyl produced.

The compound X was prepared according to the following reaction scheme:

OH PH

/ ν ^ v

OCO, CH, C, H _C

ί Δ O D

(CH ₂ ) ₄ CONH

NHCO

OCO-CH, CH- L tob

co-ch-c.h.

LL O b

(CH ₂ ) ₄ CO NH

OCO-CH, C, H _C Z 2 ο 5

A solution of 24 g of Compound I and 11.7 g of Compound II were placed in a 5 liter Morton flask containing 90 g of Na ₂ CO, and 21 g of ( ^N H ₄ ) ₂ S ₂ O ₈ dissolved in 1 Liters of H ₂ O contained. The mixture was then stirred for 1 1/2 hours and _{poured into 10 liters of H 2} O containing 2 liters of ethyl acetate. The ethyl acetate layer was then separated and washed with water and then with dilute acetic acid. The resulting red solution was then washed with MgSO. dried and filtered, and the filtrate was evaporated. In this way a solid red residue was obtained. The residue was then in a fluorosil column with chlorophore as elution

30982S / 0828

2290194

medium chromatography. It was then recrystallized from acetonitrile. 20 g of a solid red mass with a melting point of 148 to 150 ^° C. (compound 3) were obtained.

OCO ₂ CH ₂ C ₆ H ₅

(CH ₂ ) ₄ CONH-

CO ₉ CH ₀ C ^ H ₁ .
I 2 6 5

OC ₁ -H,

-n

Compound 3 was contained in 100 ml of dry tetrahydrofuran Dissolved 0.5 ml of dry pyridine, whereupon 2 ml of trifluoroacetic anhydride were added. The solution was immediate to orange. It was left to stand at room temperature for 1 hour and then dried. After recrystallization from acetonitrile, 4.7 g of a solid orange-colored compound with a melting point of "1S2 to 157 ° C. were obtained. In An approximately 0.5 liter Parr flask was filled with 150 ml of tetrahydrofuran and 1 g of a palladium-carbon catalyst as well 5 g of compound 4 are given. The connection 4 was then at room

2 temperature and a pressure of about 2.45 kg / cm for 1/2 hour. The reduction mixture was then filtered through a commercially available filter aid based on kieselguhr (Gelite) to remove the catalyst, after which the solvent was stripped off under reduced pressure. A light pink colored solid mass remained. This was recrystallized from acetonitrile. 3 g of a white solid mass with a melting point of 187 to 189 ^° C., which consisted of the compound X, were obtained.

309826/0 6'2 θ

401

Example 26

First of all, a recording material for the image transfer process was produced by applying the layers specified below to a layer support (the concentration data in each case relate to a layer support area of 0.0929 m ² ):

1) a red sensitive silver bromide iodide emulsion layer with based on silver 70 mg silver bromide iodide, 230 mg gelatin, 75 mg of the compound XXVII, dispersed in 122 mg diethyl lauramide, 10 mg 5,6,7,8-tetrahydro-5,8-methano-1,4-naphthalenediol and 7.5 mg of 5- (2-cyanoethylthio) -1-phenyltetrazole, dispersed in 22 mg of tricresyl phosphate;

2) a layer of 150 mg gelatin, 70 mg 2,5-di-sec-dodecylhydroquinone, 30 mg of the purple filter dye of the layer of Example 20 dispersed in 50 mg of diethyl lauramide;

3) a green-sensitive silver bromide emulsion layer containing 70 mg of silver, 230 mg of gelatin, 55 mg of compound XV, dispersed in 65 mg of diethyl lauramide, 10 mg of 5,6,7,8-tetrahydro-5,8-methano-1,4-naphthalenediol and 7.5 mg of 5- (2-cyanoethylthio) -1-phenyltetrazole, dispersed in 22 mg of diethyl lauramide;

4) a layer of 150 mg gelatin, 2, S-di-sec-dodecylhydroquinone and 100 mg of the yellow filter dye of layer 3 of Example 20, dispersed in 28 mg of diethyl lauramide;

5) a blue-sensitive silver bromide iodide emulsion layer with a silver halide content corresponding to 70 mg silver, 210 mg Gelatin, 46 mg of compound XXVHI dispersed in 79 mg Diethyl lauramide, 10 mg 5,6,7,8-tetrahydro-5,8-methano-1,4-naphthalenediol and 7.5 mg of 5- (2-cyanoethylthio) -1-phenyltetrazole, dispersed in 22 mg tricresyl phosphate;

30982 & / Q828

2259194

6) a layer of 50 mg gelatin *. .

The recording material obtained was then passed through a multicolor Test object exposed with graduated density levels and then exposed by bringing it into contact with an image receiving element with an image receiving layer made of 200 mg copoly / ^ styrene / N-Benzyl-NjN-dimethyl-N- (3-maleimidopropyl) ammonium chloride ^ / and 200 mg of gelatin in the presence of a developing liquid of the composition given below, consisting of a splittable container between the image receiving element and the recording material was distributed, developed.

Developing fluid

g / L

Potassium hydroxide 51

Potassium bromide 50

α-Benzyl picolinium bromide 10

Hydroxyethyl cellulose 30

After 60 seconds, the recording material and the image-receiving element became separated from each other. After which the image receiving element Exposed to air for 1 minute had a well-defined color image with excellent color properties in the Image receiving layer formed by air oxidation.

The process was repeated, but this time all of the S, 6,7,8-tetrahydro-5, S ~ methano-1,4-naphthalenediol in the cleavable Container was housed. This time too, a distinctive color image of excellent properties was obtained.

2250194

9 * "

40fr

The compounds XXVII and XXVIII had the following structural formulas:

link
XXVII

link
XXVI11

Cl

OCC F _t

Il J

OCH

CH ₃

CIL-C-CO-CH-CO-NH-CH ₃ NH

OH

NHCO (CH ₇ )

OH

OCCH,

Il J

The following describes the production of a ballast group oxichromogenic compound of the following structural formula

JQ9025 / OS28

2260134

-

C-NH (CH J ₄ -O

^c s "ii

- ^C 5 ^H 1 -t

-t

NHSO.

CONH-

0 0 / ν

C-CH-CV ^x >

described in more detail:

Intermediate connection A:

One equivalent of compound 1 of the following formula

C-NH (CH ₂ ;

-t

C ₅ H -t

link

CO ₂ H

prepared as described in US Pat. No. 3,476,563, was dissolved in 150 ml of dry tetrahydrofuran contained in a Parr hydrogenation vessel with 1 g of palladium-carbon catalyst. The compound was hydrogenated at a hydrogen pressure of 3.15 kg / cm at 25 ^° C. until 3 equivalent hydrogens had been absorbed. The reducing mixture was then filtered to remove the catalyst and the filtrate was evaporated to dryness. The solid mass obtained in this way was recrystallized from acetonitrile. A white solid residue was obtained.

Intermediate connection B:

An equivalent of compound II:

-I INC-CH-C

N-COCF.

Connection 2

prepared as described in Example 8 of US Patent Application 206,949, was contained in 20 times the volume of acetic acid 1 equivalent of dissolved acetic acid dissolved. 1 equivalent of compound 3 was then added to the solution:

Connection 3

309825/0828

22501S4

added in. granular form «The solution obtained was then Stirred for 2 hours at room temperature and then poured into water containing dissolved NaCl. A gummy mass separated out, which was filtered off and dissolved in ethyl acetate. The ethyl acetate solution was then washed with water and dried, whereupon the ethyl acetate was stripped off under reduced pressure. A light brown solid mass was obtained, which consists of Acetonitrile was recrystallized.

One equivalent each of intermediate compound A and the intermediate compound B were in 20 times the volume of dry acetone, containing 1 equivalent of Na-CO-, dissolved. The mixture obtained was then refluxed for 16 hours after which the reaction mixture was filtered. From the FiItrat it was Acetone stripped off under reduced pressure. A tar-like mass was obtained which crystallized in chlorophore and precipitated Acetonitrile could be recrystallized. The connection possessed the given structural formula.

Example 27

The prepared compound was used for the preparation of a recording material of the type known from U.S. Patent 3,227,552 for performing the diffusion transfer process used. Direct-positive silver halide emulsions were used to produce the recording material. Simultaneously an image-receiving member was prepared, the image-receiving layer thereof as a pickling agent M-n-octadecyl-tri-buty.lammonium bromide contained. Following the procedure described in Example 26, using the recording material and the image receiving element including air oxidation of the image-receiving layer, yellow positive images of excellent quality are obtained.

Similarly, magenta and cyan image dyes can be used Oxy chromogenic compounds containing ballast groups getting produced.

309821/0820

Claims (38)

ΛΑ * PATENT CLAIMS 1. Photographic recording material with a support and at least one light-sensitive layer, the light-sensitive Compound with an image dye-forming agent Connection is in contact, characterized in that it as the image dye-forming compound, an oxichromogenic compound contains one of the following formulas: (UC) -D or (OC) -link- (coupler remainder ballast group) where mean: I) an aromatic silver halide developing agent; (OC) one by chromogenic oxidation into an amino dye residue transferable remainder; the link is a residue which cleaves off upon contact with an oxidized silver halide developing agent; the coupler radical is a 5-pyrazolone, a pyrazolotriazole, a phenolic or an open-chain ketomethylene coupler radical, with the proviso that the coupler radical is substituted in the coupling position by the link; the ballast residue is a photographically inert organic residue of such a molecular size and configuration as to render the compound represented by the structural formula nondiffusible when developed with an alkaline developing solution, and η »1 or 2. JQyB25 / 0829 260194 - / ■ 2. Photographic recording material according to claim 1, dadurcli characterized as being an image dye-forming compound contains a compound of one of the specified formulas in which the remainder (OC) corresponds to the following structural formula: ■ R ² . - (Coupler residue) -N-Ar-X where mean: the coupler rest a coupler rest that is in coupling position is attached to the nitrogen atom; an arylene group having 6 to 20 carbon atoms; a hydroxy or amino radical or a radical of the formula -0-R, in which R ^{1 is} a radical of the following formula containing a carbonyl group: -C-R , 4 wherein R "is an optionally substituted alkyl or aryl radical having 1 to 12 carbon atoms is j, and is a hydrogen atom or a radical for R specified structure, where it applies that at least 1 2 at least one of the radicals R and R in the form of a a residue containing a carbonyl group is present. 3. Photographic recording material according to Claims 1 and 2, characterized in that the photosensitive compound of the light-sensitive layer or layers composed of silver halide. 3G982S / OS2S 4. Photographic recording material according to claim 2, characterized characterized in that it contains at least one compound of the formula given in which X is a hydroxyl radical, and that furthermore at least one layer of the recording material Onium salt in water-permeable contact with one of the liquid dyes generating compound contains. 5. Photographic recording material according to claim 1, characterized characterized in that it contains a compound of the formula (OC) -D which is diffusing. 6. Photographic recording material according to claim 1, characterized characterized in that it is a compound of the formula: (OC) -D contains, in which D an aromatic silver halide developing agent with at least two hydroxyl, amine and / or alkylamine radicals. 7. Photographic recording material according to claim 1, characterized characterized in that there is at least one compound of the formula: (OC) -D contains, in which D is a hydroquinone residue and (OC) is an indophenol dye residue constituent remainder is. 8. Photographic recording material according to claim 1, characterized characterized in that there is at least one compound of the formula: (OC) -Binding link- (Coupler rest- Ba Hast group) contains, in which the remainder (OC) contains at least one water-soluble Group has. JÜ982 & / 0828 JHß 9. Photographic recording material according to claim 1, characterized characterized in that the recording material has at least two, preferably three, silver halide emulsion layers, either each contain a dye-forming compound of the specified structure or with such compounds containing layers are in contact. 10. Photographic recording material according to claim 9, characterized characterized in that it has: a blue sensitive silver halide emulsion which has a contains a yellow dye-producing oxichromogenic compound or is in contact with a layer containing such a compound; a green-sensitive silver halide emulsion layer which is a contains a magenta dye-forming oxichromogenic compound or with a compound containing such a compound Layer is in contact, and a red sensitive silver halide emulsion layer containing a cyan dye-forming oxichromogenic compound contains or is in contact with a layer containing such a compound. 11. Photographic recording material according to claim 10, characterized characterized in that all dye-producing compounds all have the formula: (OC) -B
correspond. 12. Photographic recording material according to Claims 1 to II, characterized in that it has an image receiving layer. 3G982 & / 0828 AH 13. Photographic recording material according to claim 2, characterized characterized in that there is at least one image dye-forming agent Contains compound of the formula given in which Ar is a phenylene radical and in which that represented by X is Uydroxylrest is in para position to the nitrogen atom. 14. Photographic recording material according to claim 2, characterized characterized in that it contains at least one compound of the formula given in which R is a polyhalogenated alkyl radical, is preferably a trifluoromethyl radical. 15. Photographic recording material according to claims 1 to 14, characterized in that it contains at least one image dye-forming compound of the following structural formula: OH (CH ₇ ) .CONH CH. COCHCO-C-CH- Cl OCOCH- i Q U 8 2 S / 0 8 2 8 (2) Cl OC-CH ₃ OH Or 3) (CH ₂ ) CON » NHCO- NCOCF. ^C 5 ^H 11 16. Photographic recording material according to claim 1, characterized characterized in that there is at least one image dye-forming compound of the formula: (OC) -link- (coupler remainder ballast group) J0982S / 08 - / ■■■■ AAk contains, in the (OC), the link, the ballast group and η have the meaning already given and the coupler radical consists of a 5-pyrazolone, a pyrazolotriazole, an open-chain Ketomethylene or a phenolic coupler radical. 17. Photographic recording material according to claim 12, characterized characterized in that the image-receiving layer is disposed between the support and a silver halide emulsion layer. 18. Photographic recording material according to claims 12 to 17, characterized in that it has at least one layer which contains a compound capable of cleaving off a development inhibitor able. 19. Photographic recording material according to claims 1 to 17, characterized in that over the outermost silver halide emulsion layer a transparent cover sheet is arranged and that there is furthermore at least one which can be split open when pressure is applied Contains container with an aqueous developing liquid, which is arranged such that the liquid when splitting of the container is poured between the cover sheet and the outer silver halide emulsion layer. 20. Photographic recording material according to claims 1 to 19, characterized in that it forms a photographic film unit consisting of: a) the photosensitive recording material with a transparent one Film base on which are applied: (1) an image receiving layer; (2) a practically opaque, light-reflecting layer which is permeable to alkaline solutions; 309825/0 2250194 Aft (3) a red sensitive silver halide emulsion layer, the one producing a blue-green image dye Oxichromogenic compound contains or with a one such compound-containing layer is in contact, a green sensitive over halide emulsion layer, which contains a magenta image dye forming, oxichromogenic compound or with a such compound-containing layer is in contact, and a blue-sensitive silver halide emulsion layer, which contains or has an oxichromogenic compound which forms a yellow image dye Compound containing layer is in contact; b) a transparent coversheet over the silver halide emulsion layers and c) at least one splittable container with an alkaline Developing liquid, which is an opacifier or an Contains opacifying agent, with the proviso that the splittable Container is arranged so that, when pressure is applied, it gets its contents between the cover sheet and the silver halide emulsion layers able to pour » 21. Recording material according to claim 20, characterized in that that the blue-sensitive silver halide emulsion layer is further removed from the image-receiving layer than the green-sensitive silver halide emulsion layer or the red emulsion layer sensitive silver halide emulsion layer. 22. Photographic recording material according to claim 20, characterized characterized in that they are permeable to alkaline solutions, practically cloudy, light-reflecting layer made of two partial layers, namely from a titanium dioxide binder layer and a carbon black binder layer, with the titanium dioxide binder layer between the image receiving layer and the carbon black binder layer is arranged. 23. Photographic recording material according to claim 20, da- ■ characterized in that the image receiving layer is an oxidizing agent contains or is in contact with a layer containing an oxidizing agent. 24. Photographic recording material according to claim 20, characterized characterized in that the image-receiving layer contains an onium compound or with one containing such a compound Layer is in contact. 25. Photographic recording material according to claims 1 to 24, characterized in that there is at least one compound of the formula: (OC) -link- (coupler remainder ballast group) contains, in the (OC), the coupler residue, the ballast group and η have the meaning given and the link from one Azo, mercury, oxy, alkylidene, thio, dithio, azoxy, Sulfonamido, aminoalkyl, sulfonyl, sulfonyloxy, acyloxy or an imido radical. 26. Photographic recording material according to claims 1 to 25, characterized in that the photosensitive layer or layers consist of a direct-positive silver halide emulsion layer or layers exist. 27. Photographic recording material according to claim 12, characterized in that characterized in that the image-receiving layer is either arranged on a special layer support and after ßelich- 30982S / 0828 2260134 - ι Processing of the photosensitive part of the recording material can be applied to this or is arranged adjacent to the silver halide emulsion layer or layers, with the proviso that an opaque layer is arranged between the silver halide emulsion layer or layers and the image-receiving layer . - ■■ "- ■ '- ■■ -. ■ -'- ■■". 28. Photographic recording material according to Claims 1 to 27, characterized in that there is at least one, oxichromogenic Compound of the formula: (OC) -D contains, in which the remainder (OC) to each remainder D by an isolating Binding is bound, ^^ relche the resonance of the chromophores Azomethine linkage of residue (OC) effectively isolated from residue D. 29. Photographic diffusion transfer method using - ^ formation of a recording material according to claims 1 to'28, characterized in that one a) a photosensitive recording material with a Layer support and at least one silver halide emulsion layer, those with a developer compound of the formula: (OC) -D where D is an aromatic silver halide developer radical and (OC) the meaning by chromogenic oxidation has a residue that can be converted into an imino dye residue, communicates, imagewise exposed; b) that the exposed recording material with an alkaline Developing liquid to develop the exposed silver halide emulsion layer or layers treated; _ ■; ...., .- .., .. c) that at least a part of the image-wise distribution diffusing present diffusing developer compound in the image-receiving layer and that one d) the developer compound diffused into the image receiving layer oxidized. 30. The method according to claim 29, characterized in that after the imagewise exposure, the oxichromogenic developer compound brings into contact with an onium compound. 31. The method according to claim 29 and 30, characterized in that a recording material is used which contains an onium compound in the image receiving layer. 32. The method according to claim 29, characterized in that the development stage b) is effected by (1) on the layer of the light-sensitive layer furthest away from the support Element applying an image-receiving layer arranged on a layer support; (2) between the exposed photosensitive recording material and the image receiving layer comprises a splittable container containing an alkaline developing liquid brings in and that one (3) exerts pressure on the container, splitting it so that its contents are between the outermost Layer of light-sensitive material and the image-receiving layer poured. 33. The method according to claim 31, characterized in that 1.) a recording material with a transparent layer support used that 2.) the image-receiving layer between the support and the silver halide emulsion (s) 309826/0828 AX * layers, 3.) that one between the outermost layer of the photosensitive element and a transparent cover sheet a splittable container with an alkaline developing liquid and that 4.) by applying pressure, the alkaline developing liquid between the photosensitive Element and transparent cover sheet distributed. 34. The method according to claims 29 to 33, characterized in that a recording material with at least one one Development inhibitor used in freedom-releasing compound. 35. The method according to claim 34, characterized in that there is a development inhibitor liberating a compound a mercaptan-releasing compound as a development inhibitor used. 36. The method according to claims 29 to 35, characterized in that that the development of the exposed silver halide emulsion layer or layers with an alkaline developing liquid in the presence of a slowly diffusing auxiliary developing agent performs. 37. The method according to claim 36, characterized in that the Bringing auxiliary developer compound in the developing liquid to the application. 38. Photographic recording material according to claims 1 to as well as 27 and 28, characterized in that the light-sensitive layer or layers consist of a negative silver halide emulsion layer, or layers exist. 3U982B / 08 28